Composition containing quaternary amino-functional organosilicon compounds and production and use thereof

ABSTRACT

The invention relates to a composition and to a method for the production thereof, comprising quaternary amino-functional organosilicon compounds, in particular in the form of oligomers and polymers, which can be present ranging from partially hydrolyzed form to completely hydrolyzed form, and which are in particular soluble in water, have a low VOC content, and to the use thereof.

The invention relates to a novel aqueous composition and processes forits production comprising quaternary amino-functional organosiliconcompounds, particularly in the form of oligomers and polymers, which canbe present in partially hydrolyzed to completely hydrolyzed form, andparticularly are water-soluble, and the compositions have only anextremely low VOC content, and also the use thereof, particularly—butnot exclusively—in papercoating slips, for cationization of inkjetcoatings, for finishing fiber materials and/or textiles, for improvingthe dyeability of substrates, for example in the case of textile fibers,yarns, paper, foils or else correspondingly coated substrates, forinhibiting/suppressing the growth of microorganisms or an electrostaticcharge buildup to mention but a few particularly advantageouspossibilities for use.

In general, organofunctional alkoxysilanes with quaternary nitrogenfunctionality, i.e., with a cationic group containing anorganofunctionalized nitrogen, are well known. The quaternary nitrogenhas a cationic functionality irrespective of the pH. Hitherto,preparation thereof was only possible via costly and inconvenientprocesses, for example under elevated pressure in an autoclave. Afurther disadvantage of these alkoxysilanes is the release of hydrolysisalcohols into the environment in the course of their use of knownwater-based application solutions.

The preparation of cationic organosilanes and their partial use inaqueous phases is reported in the following documents. DE 881654discloses the preparation of quaternary silanes in an autoclave underanhydrous conditions. Further processes are disclosed by NL 6517163 forpreparing quaternary methylarylsilanes, DE 1262272 discloses thepreparation of corresponding silicones. Similarly, DE 2221349, DE2648240, U.S. Pat. No. 4,035,411, U.S. Pat. No. 4,005,118 and U.S. Pat.No. 4,005,119 disclose processes for preparing quaternary silanes.

The use of quaternary amino-functional alkoxysilanes for inhibiting thegrowth of microorganisms is described by DE 2222997, DE 2229580 and DE2408192. An improved dyeability of difficult-to-dye materials, such asTeflon or else leather, through using corresponding silanes is disclosedby GB 882067. The preparation of quaternary functionalized organosilanesis in each case effected in aprotic organic solvents or under moistureexclusion and under elevated pressure. The silanes prepared by theseprocesses, or aqueous formulations thereof, contain large amounts ofsolvent. This leads in many applications to appreciable disadvantages,such as a low flashpoint, which requires explosion protection, orcreates a cause of environmental damage through a high VOC burden.

EP 0054748 discloses a process wherein for example3-chloropropyltriethoxysilane is reacted with aqueous trimethylamine astertiary amine in an autoclave under elevated pressure. The reactionneeds to be carried out under elevated pressure in an autoclave becauseof the necessary high reaction temperature of 120° C. or higher. Thewater-based formulations contain appreciable amounts of VOC through useof alkoxy-functional silanes and alcohol-water mixtures as solvents.Examples 1, 2, 3, 6, 7, 8, 9 and 10 suggest that VOC contents in thefinal formulations are between about 16% and 40% by weight. Examples 4,5 and 11 proceed from, respectively bromoalkyl- and iodoalkyl-functionalorganosilanes and can be regarded as industrially irrelevant because ofthe environmental issues associated with the remaining counter-anionsiodide and bromide.

WO 2008/076839 utilizes a commercially available quaternary silane (AEM5772, Aegis Antimicrobial agent, active ingredient:3-(trimethoxysilyl)propyldimethyl-octadecylammonium chloride), whichcontains 12% of methanol. U.S. Pat. No. 4,845,256 discloses a processfor preparing quaternary silanes alkaline earth metal iodide catalystsfor the reaction of chloroalkyl-functional alkoxysilanes and tertiaryamines. The process described proceeds under normal pressure at atemperature of 100° C., but is disadvantageous in two respects. First,the environmentally problematical alkaline earth metal iodides are usedin appreciable amounts; secondly, the aqueous application solutionscontain appreciable amounts of VOC, such as hydrolysis methanol andglycols which are used in the process therein and remain in theapplication solution. The product described in example 1 generates morethan 50% of VOC in an aqueous application solution (based on thestarting solution of the quaternary methoxysilane[3-(trimethoxysilyl)propyldecyldimethylammonium chloride] dissolved inpropylene glycol monomethyl ether).

The following documents disclose the use of cationic amino-functionalsilanes for cationization of inkjet paper applications.

WO 2005/009745 A2 discloses cationic aluminum oxide particles withamino-functional silanes. US 20030175451 relates to the coating ofsilica with silanes to improve performance in inkjet applications. US20050170109 discloses the treatment of silica with aminoalkoxysilanesand use thereof for inkjet papers and DE 10 2007 012578 A1 discloses thepreparation of cationic silica dispersions using primary, secondary ortertiary aminosilanes and use thereof for coatings. WO 2005/009745 A2,US 2005/170109 A1 and US 2003/175451 mention in general the possibilityof using a quaternary amino-functional alkoxysilane, such astrimethoxysilanepropyl-N,N,N-trimethylammonium chloride, or anN,N,N-tributylammonium chloride-substituted silane. Concrete examplesare not disclosed.

DE 102007040802 A1 describes the successful use of low-VOC, protonatedamino-functional silanol group-containing siloxane systems (hydrosils)in the cationization of papercoating slips. The protonation of the aminofunction of these systems is substantially pH-dependent. Therefore, theperformance of these applications is still in need of improvement. Theprocessability of papercoating slips is governed by their viscosity andsolids content. The higher the viscosity, the greater the inconvenienceand cost of processing, although at the same time a high solids contentis desired for the systems for capacity reasons.

There accordingly continues to be a need for VOC-reduced quaternaryamino-functional organosilicon compounds which make it possible to set alow viscosity coupled with a simultaneously high solids content ofdispersions, for example silica dispersions, more particularlypapercoating slips.

The problem addressed by the present invention was that of providingVOC-reduced quaternary aminoalkyl-functional organosilicon compounds, orcompositions containing these, and also an economical process forproduction thereof which preferably permits an economical setting of thedesired viscosity and of the solids content in the process.

The problem is solved according to the present invention in accordancewith the recitations in the claims. More particularly, the problem issolved by the inventive composition corresponding to the features ofclaims 16 and 21 and also by the inventive production process accordingto claim 1. Preferred embodiments are recited in the dependent claimsand also in the description.

The problem was solved, surprisingly, by reacting haloalkyl-functionalalkoxysilanes, optionally together with further organofunctional siliconcompounds, such as organofunctional alkoxysilanes and/orcondensation-capable oligomeric or polymeric organofunctional siliconcompounds, together with tertiary amines in the presence/under additionof a defined amount of water and removing the resulting hydrolysisalcohol at least partially and preferably removing the hydrolysisalcohol essentially completely. The occurring quaternization reactionand at least partial hydrolysis and any partial condensation, i.e.,including co- or block condensation, is advantageously carried out undertemperature control, i.e., heating or cooling is applied as necessary,and the reaction mixture is suitably stirred. In the process, anoriginally tertiary organofunctionally substituted nitrogen atom of thetertiary amine becomes a quaternary nitrogen atom, more particularly byformation of oligomeric or polymeric quaternary amino-functionalorganosilicon compounds which are obtainable according to the presentinvention and which are more particularly elucidated hereinbelow.

Furthermore, hydrolysis alcohol formed during or after the hydrolysisreaction can be distillatively removed from the aqueous reaction mixtureand fresh water added as necessary, in which case the present inventionprovides an aqueous solution of said quaternary amino-functionalorganosilicon compounds, preferably quaternary alkylammonium-functionalorganosilicon compounds (hereinafter also referred to as composition orsilane system for short) which is ready to use or suitable foradvantageous application.

Subject compositions advantageously have a VOC content of distinctlybelow 12% by weight to 0% by weight, based on the overall composition.The content of volatile organic compounds (VOCs), more particularlysolvents, such as hydrolysis alcohol, in a composition according to thepresent invention is preferably below 5% by weight, more preferablybelow 2% by weight, even more preferably below 1% by weight and moreparticularly in the range from 0.001 to 0.5% by weight, based on theoverall composition. Therefore, subject compositions are hereinafteralso referred to as VOC-free for short. Furthermore, the compositionsobtainable according to the present invention, which contain quaternaryaminoalkyl-functional organosilicon compounds, are thinnable with waterin virtually any ratio, more particularly between 1:100 to 100:1 andalso all ratios therebetween.

The quaternary amino-functional organosilicon compounds can be moreparticularly oligomeric/polymeric organosilicon compounds which, permolecule, include at least one quaternary aminoalkyl-functional radical,more particularly at least one quaternary alkylammonium-functionalradical, in which case at least one of the aminoalkyl radicals comprisesa silicon atom, more particularly a silanol group or an organosilanol,an oligomer or polymer of organosilicon compounds.

The invention is an advantageous way of providing novel VOC-reduced(volatile organic compound) organofunctional silane systems, hereinbelowcalled compositions, with quaternary nitrogen functionality (NR₄ ⁺,where the R groups can be the same or different and at least one R groupis silylated and R is covalently bonded to N via a C-atom), which areadvantageously providable at normal pressure and in high yield. At leastone R radical comprises organosilicon groups, optionally R may alsocontain further heteroatoms. Altogether, the silane system according tothe present invention may evince linear, branched, cyclic and/orspatially crosslinked structures or structural regions with M-, D-,T-structures or else, depending on the method of making, Q-structures.When tetraalkoxysilane is added to the reaction mixture, for example.

Condensation products for the purposes of the invention comprehend notonly homo-but also co-condensation products from the reaction ofhydrolyzed alkoxysilanes, silanols, oligomeric or else polymericSiOH-functional silicon compounds or organosilicon compounds, and alsocondensation products involving the participation of blockco-condensates.

It is further surprising that the reactions mentioned as taking place inthe course of the process of the present invention, such asquaternization, hydrolysis and, where applicable, condensation, can becarried out virtually simultaneously in one reaction mixture atrelatively low reaction temperatures below 100° C. and henceparticularly advantageously. A further particular advantage of theprocess according to the present invention is that the conversion cantake place at these relatively low temperatures at normal pressure.Therefore, the use of costly and inconvenient autoclaves is unnecessaryin the process of the present invention, since, depending on thetertiary amines used and their boiling point, the reaction isadvantageously carried out at normal pressure when the boiling point ofthe amines is above the reaction temperature. The boiling point of thetertiary amines used, particularly of formula II, as elucidatedhereinbelow, is preferably above 85° C., more preferably above 100° C.and more particularly above 120° C.

It is particularly surprising that not only the quaternization reactionat the haloalkyl group of the starting haloalkyl-functional silane offormula I but also the hydrolysis and also condensation/co-condensationof the organosilicon compounds in the reaction mixture take place notjust simultaneously, i.e., as a one-pot reaction, but moreover alsosubstantially selectively.

Surprisingly, the problem was solved by a process for preparing aninventive composition containing quaternary aminoalkyl-functionalorganosilicon compounds by reacting,

-   -   at least one haloalkyl-functional silane of formula I and/or        optionally its hydrolysis and/or condensation products, i.e.,        including possible homo-, co-, block or block co-condensates,

(R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (I),

-   -   -   where the R¹ groups are the same or different and R¹            represents a hydrogen, a linear, branched, or cyclic alkyl            group having 1 to 8 carbon atoms, an aryl, arylalkyl or acyl            group,        -   the R² groups are the same or different and R² represents a            linear, branched or cyclic alkyl group having 1 to 8 carbon            atoms, an aryl, arylalkyl or acyl group, the R³ groups are            the same or different and R² signifies a linear, branched or            cyclic alkylene group having 1 to 18 carbon atoms, i.e., a            bivalent alkyl group having 1 to 18 carbon atoms, wherein            the alkylene group may be substituted or contain olefinic            C—C linkages, preferably —CH₂—, —(CH₂)₂—, —CH₂CH(CH₃)—, n is            equal to 0 or 1 and Hal represents chlorine or bromine, and        -   x is equal to 0, 1 or 2, y is equal to 0, 1 or 2 and (x+y)            is equal to 0, 1 or 2,

    -   with a tertiary amine of the general formula II

    -   in the presence and/or under addition of a defined amount of        water,

N(R⁴)₃  (II),

-   -   -   where the R⁴ groups are the same or different and R⁴            represents a group            (R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂—]_(1+y), where R¹, R²,            R³, n, x, y and (x+y) likewise have the aforementioned            meaning, or represents a linear, branched or cyclic alkyl            group having 1 to 30 carbon atoms which may additionally be            substituted, preferably with at least one group from the            series —N(R⁵)₂, where the R⁵ groups are the same or            different and R⁵ represents a hydrogen, a linear, branched            or cyclic alkyl group having 1 to 8 carbon, atoms, an            aminoalkyl group or            (R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂—]_(1+y),        -   —SR⁶, where the R⁶ groups are the same or different and R⁶            represents a hydrogen, a linear, branched or cyclic alkyl            group having 1 to 8 carbon atoms or            (R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂—]_(1+y), or optionally            its hydrolysis and/or condensation products, —OR¹ or        -   (R¹0)_(3-x)(R²)_(x)Si[(R³)_(n)CH₂—] or optionally its            hydrolysis and/or condensation products, where the groups            R¹, R², R³, x and n independently have the meaning already            mentioned above,        -   where optionally two R⁴ groups are in turn linked together            and combine with the nitrogen of the tertiary amine to form            a cycle,

    -   and the resultant hydrolysis alcohol is at least partially        removed.

In addition, however, the subject process can also utilize furthercomponents, for example as a catalyst, as a diluent or as an inputcomponent—to mention but a few of the possibilities.

The present invention accordingly provides a process for preparing acomposition containing quaternary amino-functional organosiliconcompounds, characterized in that it comprises reacting

-   -   as component A    -   (i) at least one haloalkyl-functional alkoxysilane of the        general formula I

(R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (I),

-   -   -   where the R¹ groups are the same or different and R¹            represents a hydrogen, a linear, branched, or cyclic alkyl            group having 1 to 8 carbon atoms, an aryl, arylalkyl or acyl            group,        -   the R² groups are the same or different and R² represents a            linear, branched or cyclic alkyl group having 1 to 8 carbon            atoms, an aryl, arylalkyl or acyl group,        -   the R³ groups are the same or different and R² signifies a            linear, branched or cyclic alkylene group having 1 to 18            carbon atoms, n is equal to 0 or 1 and Hal represents            chlorine or bromine, and        -   x is equal to 0, 1 or 2, y is equal to 0, 1 or 2 and (x+y)            is equal to 0, 1 or 2,

    -   or

    -   (ii) a hydrolysis or condensation product of at least one        alkoxysilane of the aforementioned general formula I

    -   Or

    -   (iii) a mixture of at least one alkoxysilane of the        aforementioned general formula I and a hydrolysis and/or        condensation product of at least one alkoxysilane of the        aforementioned general formula I

    -   with a tertiary amine of the general formula II as component B,

N(R⁴)₃  (II),

-   -   -   where the R⁴ groups are the same or different and R⁴            represents a group            (R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂—]_(1+y), where R¹, R²,            R³, n, x, y and (x+y) likewise have the aforementioned            meaning, or represents a linear, branched or cyclic alkyl            group having 1 to 30 carbon atoms which may additionally be            substituted, where optionally two R⁴ groups are in turn            linked together and combine with the nitrogen of the            tertiary amine to form a cycle,

    -   in the presence of a defined amount of water, and

    -   removing the resulting hydrolysis alcohol at least partially        from the system.

According to the present invention, it is advantageously a silane offormula I, more particularly a chloroalkyl-functional silane optionallyits hydrolysis and/or condensation product, which is mixed in theprocess with a tertiary amine of formula II, there ensues in thepresence of 0.5 to 500 mol of water per mol of silicon atoms aquaternization—on the nitrogen atom—and at least partially hydrolysisand possibly condensation (of the alkoxysilanes to silanol groups,followed by a condensation to form Si—O—Si bridges)—of the compounds offormula I and II. The reaction can preferably be carried out in a kindof “one-pot reaction”, for example batchwise, hydrolysis alcohol can bedistilled off during the reaction and further water added at essentiallythe same time. The pressure in the reaction vessel can also be reducedwith increasing reaction duration, i.e., the volatile organic fractions,more particularly the hydrolysis alcohol which is formed, can beremoved, at least proportionally, from the system by distillation underreduced pressure.

Furthermore, the reaction mixture of components A and B may have addedto it as a further input component C, at least one further hydrolyzablesilicon compound, preferably an organoalkoxy-functional siliconcompound, its hydrolysis, homo-, co-, block co-condensate or mixturesthereof.

The inventive quaternization reaction, hydrolysis and at least partiallyensuing condensation, i.e., including possible, homo-, co-, block orblock co-condensation, will make oligomeric and/or polymericorganosilicon compounds having at least one quaternaryalkylammonium-functional radical or else cyclic compounds withquaternary nitrogen, for example an N-alkylpyrimidinium compound,obtainable according to chemical understanding.

According to the present invention, the process is carried out in thepresence and more particularly under addition of a defined amount ofwater in that more particularly 5 to 25 mol of water per mol of siliconatoms are added, preferably 10 to 20 mol of water per mol of siliconatoms and more preferably 12 to 17 mol of water per mol of siliconatoms. In general, the water can be added continuously ordiscontinuously, in which case it will prove particularly advantageousto add the water discontinuously, preferably portionwise, specificallyin 1 to 10 portions, preferably 2 to 5 portions and more preferably in 3portions. The process of the present invention thus preferably utilizeswater in an amount of 0.5 to 500 mol of water per mol of silicon atomspresent in the reaction mixture, preferably 5 to 25 mol of water permole of hydrolyzable silicon atoms concerning the used components A andalso optionally B and/or C, particularly preferably 10 to 20 mol ofwater per mol of said silicon atoms, more particularly 12 to 17 mol ofwater per mol of said silicon atoms. It is further preferable in theprocess of the present invention when the water is metered continuouslyor discontinuously into the reaction mixture of the input components A,B and optionally C, in particular the water is added discontinuouslyunder stirring, more preferably portionwise, in 1 to 10 portions, moreparticularly in 2 to 5 portions. It is further preferable, in theprocess, for the water to be added as rapidly as possible to the silaneof formula I, the tertiary amine of formula II or the mixture comprisingthe silane and the amine. Surprisingly, the time and/or the portionwiseaddition of the water can also have a particularly good influence on theviscosity of the composition with an otherwise unchanged content ofquaternary amino-functional organosilicon compounds. Preferably, theaddition of water takes place very directly subsequent to mixing thecompounds of formula I and II. Adding the entire amount of water in onestep to the reaction can lead to the formation of insoluble precipitateswhich have to be expensively and inconveniently filtered off to producesolutions of the composition for example.

More particularly, the reaction according to the invention is carriedout at a pressure of 1 mbar to 1.1 bar, preferably at ambient pressure(normal pressure), and a temperature of 20 and 150° C., preferably inthe range from 40 to 120° C., more preferably in the range from 60 to100° C. and more particularly in the range from 80 to 95° C. It isparticularly preferable to perform the reaction at a reactiontemperature below 100° C. and at normal pressure, more particularlyaround 1013.25 hPa plus/minus 25 hPa.

The present reaction can also be carried out in the presence of acatalyst, more particularly under addition of a hydrolysis and/orcondensation catalyst, for example—but not exclusively—an organic orinorganic acid, such as formic acid, acetic acid, propionic acid, citricacid, hydrogen chloride, as gas, concentrated or aqueous hydrochloricacid, boric acid, nitric acid, sulfuric acid, phosphoric acid to namebut a few.

In addition, to carry out the reaction, the reaction mixture ofcomponents A and B or a reaction mixture of components A, B and at leastone further component C can have added to it a diluent, for example analcohol, such as methanol, ethanol, isopropanol, in which case thediluent added is suitably removed again from the system as it were inthe course of the removal of the hydrolysis alcohol formed in the courseof the reaction.

The hydrolysis alcohol formed in the course of the reaction is removedessentially completely, preferably by distillation, more particularlyduring the reaction. In a particularly preferred process mode, thedistillatively removed amount of hydrolysis alcohol and water can becompensated in the azeotropic mixture by further addition of water, say.

Advantageously, in the process of the present invention, volatilesolvent/diluent medium and any groups hydrolyzable to volatile solvent,more particularly hydrolysis alcohol, are removed down to a level in theoverall composition of below 12% by weight to 0% by weight, preferablybelow 10% by weight, more preferably below 5% by weight and even morepreferably in the range from 2% by weight to 0.0001% by weight and moreparticularly in the range from 1% to ≦0.5% by weight, wherein theremoving of volatile solvent/diluent medium can be effected during thereaction and/or thereafter by distillation, more particularly underreduced pressure in the range from 1 to 1000 mbar and preferably from 80to 300 mbar. Suitably, however, the pressure can also be lowered in thecourse of the reaction from ambient pressure to a reduced pressure.

The purely quaternization reaction of compounds of formula I, or as percomponent A and of the tertiary amine of formula II as per component Bto form at least one said quaternary aminoalkyl-functional silane isshown in idealized form in what follows, wherein the formulae I and IIare as defined above:

Furthermore, during the reaction, hydrolysis and also condensation ofcompounds of formulae I, II and/or resultant quaternization products(IV) can lead to the formation of so-called oligomeric and/or polymericquaternary amino-functional organosilicon compounds as elucidatedhereinbelow.

It is believed, in common with chemical understanding, that, under thereaction conditions according to the present invention, the reaction ofcompounds of formulae I and II proceeds by quaternization and at leastpartial hydrolysis, as idealized hereinbelow (the R groups may be alkylor aminoalkyl, for example—but nonexclusively—methyl, ethyl, propyl,butyl, N,N-dimethylaminoethyl):

Quaternization and partial/complete hydrolysis:

Cl—(CH₂)₃—Si(OEt)₃+(R)₃N+H₂O->Cl⁻(R)₃N⁺—(CH₂)₃—Si(OEt)₂(OH)+EtOHCl—(CH₂)₃—Si(OEt)₃+(R)₃N+2 H₂O->Cl⁻(R)₃N⁺—(CH₂)₃—Si(OEt)(OH)₂+2 EtOHCl—(CH₂)₃—Si(OEt)₃+(R)₃N+3 H₂O->Cl⁻(R)₃N⁺—(CH₂)₃—Si(OH)₃+3 EtOH

Condensation:

x Cl⁻(R)₃N⁺—(CH₂)₃—Si(OH)₃->

[(HO—)₂Si(—CH₂)₃—N⁺(R)₃)—[O—Si((—(CH₂)₃—N⁺(R)₃)(OH)]_(x-2)—O—Si(—(CH₂)₃—N⁺(R)₃)(OH)₂].xCl⁻+x H₂OCl⁻(R)₃N⁺—(CH₂)₃—Si(OEt)(OH)₂+xCl⁻(R)₃N⁺—(CH₂)₃—Si(OH)₃->[EtOSi(OOH)(—(CH₂)₃N⁺(R)₃)—[O—Si(—(CH₂)₃N⁺(R)₃(OH))]_(x-1)—O—Si((—CH₂)₃N⁺(R)₃)(OH)₂].(x+1)Cl⁻+(x+1)H₂Ox can be a number from 2 to ∞.

It is particularly preferable for the inventive reaction of silanes offormula I within the meaning of component A with tertiary amines offormula II as component B, optionally in the presence of at least onesilicon compound of formula III as component C of the reaction mixture,in the process of the present invention to take place exclusively in thepresence of moisture or water, in which case hydrolysis, homo- and/orco-condensation products of II and optionally III are also encompassedand from 0.5 mol to 500 mol and more preferably from 0.5 to 200 mol ofwater are preferably used per mol of silicon.

Component A in the process of the present invention may advantageouslycomprise for example—but not exclusively—a silicon compound from theseries 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,3-chloropropylmethyl-dimethoxysilane,3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethyl-ethoxysilaneor 3-chloropropyldimethylmethoxysilane or a hydrolysis or condensationproduct of the aforementioned alkoxysilanes.

In general, any compounds which are known to a person skilled in the artas containing tertiary amino groups are useful as component B forproducing the composition of the present invention, preferably whentheir boiling point is above 85° C. and more preferably when theirboiling point is above 100° C. or above 120° C.

One particular advantage of the process according to the presentinvention is the low reaction temperature, which is between 20 to 150°C., more particularly between 40 to 120° C., preferably between 60 to100° C. and more preferably between 80 to 95° C., and the reaction ispreferably carried out essentially at normal pressure. According to thepresent invention, the reaction can be carried out at a temperaturebelow 100° C. and preferably at normal pressure.

Component B in the process of the present invention may advantageouslycomprise for example—but not exclusively—at least one tertiary amineselected from the series tetramethylethylenediamine,pentamethyldiethylenetriamine, hexadecyldimethylamine,octadecyldimethylamine, tetradecyldimethylamine, dodecyldimethylamine,decyldimethylamine, octyldimethylamine, tetraethylethylenediamine,pentaethyldiethylenetriamine, hexadecyldiethylamine,octadecyldiethylamine, tetradecyldiethylamine, dodecyldiethylamine,decyldiethylamine, octyldiethylamine, isohexadecyldimethylamine,isooctadecyldimethylamine, isotetradecyldimethylamine,isododecyldimethylamine, isodecyldimethylamine, isooctyldimethylamine,isotetraethylethylenediamine, isopentaethyldiethylenetriamine,isohexadecyldiethylamine, isooctadecyldiethylamine,isotetradecyldiethylamine, isododecyldiethylamine, isodecyldiethylamine,isooctyldiethylamine, tris(trimethoxysilylpropyl)amine,tris(triethoxysilylpropyl)amine, tris(trimethoxysilylmethyl)amine,tris(triethoxysilylmethyl)amine.

The reaction of the haloalkyl-functional silane, more particularly thechloroalkylsilane of formula I, is preferably carried out using a molarratio of haloalkyl group to tertiary amine group, more particularly ofan amine of formulae II, V and/or VI, in the range from 2:1 to 1:m,where m is the number of tertiary amine groups, and more particularly mis an integer between 1 to 100. It is accordingly preferable for theprocess of the present invention when components A and B are used in aratio, wherein the molar ratio of the silicon compound within themeaning of formula I to the tertiary amine compound within the meaningof formula II is in the range from 2:1 to 1:m, wherein m is the numberof tertiary amine groups of formula II and m is an integer between 1 to100, preferably in the range from 1 to 10, more preferably 1, 2, 3, 4,5, 6 or 7 and more particularly 1 or 2.

In addition, the process of the present invention can be advantageouslyutilized in components A and C, which will be further particularizedhereinbelow, in a molar ratio of 1:<4, preferably 1:0 to 2, morepreferably 1:0.001 to 1 and more particularly 1:0.1 to 0.5.

Component C in the process of the present invention can comprise forexample—but not exclusively—at least one silicon compound from theseries silicon tetrachloride, tetramethoxysilane, tetraethoxysilane,tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxy-silane,n-propyltriethoxysilane, n-butyltrimethoxysilane,i-butyltrimethoxysilane, n-butyltriethoxysilane, i-butyltriethoxysilane,n-octyltrimethoxysilane i-octyltrimethoxy-silane,n-octyltriethoxysilane, i-octyltriethoxysilane,hexadecyltrimethoxysilane, hexadecyltriethoxysilane,vinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(2-methoxyethoxy)silane, phenyltrimethoxysilane,phenyltriethoxysilane,tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane,tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxy-silane,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,1-mercaptomethyltrimethoxysilane, 1-mercaptomethyltriethoxysilane,3-glycidyloxy-propyltriethoxysilane,3-glycidyloxypropyltrimethoxysilane,3-methacryloxyisobutyl-trimethoxysilane,3-methacryloxyisobutyltriethoxysilane,3-methacryloxypropyl-trimethoxysilane,3-methacryloxypropyltriethoxysilane,3-methacryloxypropylmethyl-dimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-ureidopropyl-triethoxysilane, 3-ureidopropyltrimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-aminopropylmethyldimethoxysilane, 3-aminopropyl-methyldiethoxysilane,1-aminomethyltrimethoxysilane, 1-aminomethyltriethoxysilane,2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane,3-aminoisobutyl-trimethoxysilane, 3-aminoisobutyltriethoxysilane,N-n-butyl-3-aminopropyl-triethoxysilane,N-n-butyl-3-aminopropylmethyldiethoxysilane,N-n-butyl-3-aminopropyltrimethoxysilane,N-n-butyl-3-aminopropylmethyldimethoxysilane,N-n-butyl-1-aminomethyltriethoxysilane,N-n-butyl-1-aminomethylmethyldimethoxy-silane,N-n-butyl-1-aminomethyltrimethoxysilane,N-n-butyl-1-aminomethyl-methyltriethoxysilane,benzyl-3-aminopropyltrimethoxysilane,benzyl-3-aminopropyltriethoxysilane,benzyl-2-aminoethyl-3-aminopropyltrimethoxysilane,benzyl-2-aminoethyl-3-aminopropyltriethoxysilane,N-formyl-3-aminopropyltriethoxy-silane,N-formyl-3-aminopropyltrimethoxysilane,N-formyl-1-aminomethylmethyl-dimethoxysilane,N-formyl-1-aminomethylmethyldiethoxysilane,diaminoethylene-3-propyltrimethoxysilane,diaminoethylene-3-propyltriethoxysilane,triaminodiethylene-3-propyltrimethoxysilane,triaminodiethylene-3-propyltriethoxysilane,(2-aminoethyl-amino)ethyltrimethoxysilane,(2-aminoethylamino)ethyltriethoxysilane,(1-aminoethyl-amino)methyltrimethoxysilane,(1-aminoethylamino)methyltriethoxysilane,tris(trimethoxysilylpropyl)amine, tris(triethoxysilylpropyl)amine,tris(trimethoxysilyl-methyl)amine, tris(triethoxysilylmethyl)amine,bis(trimethoxysilylpropyl)amine, bis(triethoxysilylpropyl)amine,bis(diethoxymethylsilylpropyl)amine,bis(dimethoxy-methylsilylpropyl)amine, bis(triethoxysilylmethyl)amine,bis(trimethoxysilyl-methyl)amine, bis(diethoxymethylsilylmethyl)amine,bis(dimethoxymethylsilyl-methyl)amine,

(H₃CO)₃Si(CH₂)₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃,(H₃CO)₃Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃,(H₃CO)₂(CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₂(CH₃),

(H₃CO)₃ (CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₂ (CH₃),or a mixture of at least two of the aforementioned compoundsor a hydrolysis/condensation product of one of the aforementionedcompoundsor a hydrolysis, condensation, co-, block or block co-condensationproduct of at least two of the aforementioned compounds.

The hydrolysis alcohol formed by hydrolysis in the course of thereaction in the process of the present invention and optionally addedsolvent/diluent medium, is suitably removed by distillation, and it ispreferable to add further water in order, more particularly, that thepreviously distillatively removed amount of water, hydrolysis alcoholand solvent may be essentially replaced. Alternatively, any desiredamount of water can be added. The distillation is preferably carried outunder reduced pressure in the range between 0.01 to 1000 mbar, moreparticularly between 1 to 1000 mbar and preferably between 80 to 300mbar. The solvent or hydrolysis alcohol is removed from the reactionmixture until the composition has a content of volatile solvent, such ashydrolysis alcohol, and any groups hydrolyzable to volatile solvent,such as alkoxy groups, of below 12% by weight to 0% by weight in theoverall composition, more particularly below 12% by weight to 0.0001% byweight, preferably below 10% by weight to 0% by weight, more preferablybelow 5% by weight to 0% by weight, even more preferably below 2% byweight to 0% by weight, to below 1% to 0% by weight. It is particularlypreferable for the volatile solvent content of the total composition tobe between 0.5% to 0.001% by weight.

Volatile solvents, or groups hydrolyzable to volatile solvents, are tobe understood as meaning alcohols, such as methanol, ethanol,isopropanol, n-propanol, and alkoxy groups which hydrolyze to alcohols,acyloxy-containing radicals and also the hydrolysis-derived acetic acidor formic acid, or else aryloxy groups capable of forming phenols andalso glycols as well as partially etherified glycols, such as ethyleneglycol, diethylene glycol or methoxyethanol, which can either be addedto the formulation or are formed by hydrolysis of their silyl esters.

It is particularly preferable for the process of the present inventionto utilize a tertiary amine of the general formula II,

N(R⁴)₃  (II)

where each R⁴ independently is a linear, branched and/or cyclicsubstituted or unsubstituted alkyl group having 1 to 30 carbon atoms,optionally substituted with one or more —NR⁵ ₂—, —OR¹— and/or —SR⁶groups, with each R¹ being independently hydrogen or R⁴; R⁶ is an alkylor alkenyl group having 1 to 30 carbon atoms; and/or one, two or threeR⁴ groups are each independently (R¹0)_(3-x)(R²)_(x)Si[(R³)_(n)CH₂—],where R¹, R², R³, x and n are each as defined above, or optionally itshydrolysis and/or condensation products. Advantageously, at least one R⁴may comprise at least one oligomeric organofunctional silanol orco-condensate, block co-condensate, more particularly R⁴ comprises a(-0_(1/2)-)_(3-x)(R²)_(x)Si[(R³)_(n)CH₂—] radical in an organosiliconcompound obtained by condensation.

Alternatively, two R⁴ groups in the form of (R⁴)₂ can combine with aheteroatom N, S or O to form cycle or heteroaromatic having 1 to 7carbon atoms, such as for example but not exclusively pyrrole, pyridine,etc.

Further tertiary amines or amino compounds useful for preparing thequaternary amino-functional organosilicon compound in order thatcorresponding products may be formed are disclosed hereinbelow.

By way of tertiary amines, more particularly of formula II, it isparticularly preferable to use amines having a boiling point above 85°C. and/or particularly amines selected from the following group, such asamines of formula IIa, IIb and/or an amine having a radical of formulaIIc and/or of formula IId, for example with IIc or IId as a B group ofthe silane of general formula III, and/or compounds derived therefrom.

According to the present invention, the tertiary amine of formula IIused in the process may likewise advantageously be an amine selectedfrom the formulae IIa and IIb,

(R¹⁴)₂N[CH₂CH₂N(R¹⁴)]_(h)CH₂CH₂N(R¹⁴)₂  (IIa),

where R¹⁴ in each occurrence is independently a branched, unbranchedand/or cyclic alkyl, aryl, more particularly benzyl, or alkylaryl having1 to 20 carbon atoms, in this case R¹⁴ is preferably methyl or ethyl,and more preferably methyl, and h is equal to 0, 1, 2, 3, 4, 5, 6 or 7,more particularly h is equal to 0, 1, 2, 3 or 4; IIa is preferablytetramethylethylenediamine or pentamethyldiethylenetriamine; when R¹⁴ ismethyl (CH₃), IIa is (CH₃)₂N[CH₂CH₂N(CH₃)]_(h)CH₂CH₂N(CH₃)₂;

[(CH₃)—(CH₂)_(w)]_(p*)N(R¹⁴)_(3-p*)  (IIb),

where w is equal to 2 to 20, more particularly w is equal to 8 to 14,and R¹⁴ is as defined above, p* is equal to 1 or 2, as particularly indioctylmethylamine, di-n-nonylmethylamine, di-n-decylmethylamine,di-n-undecylmethylamine, di-n-dodecyl-methylamine,di-n-tridecylmethylamine or di-n-tetradecylmethylamine.

It is particularly preferable to use tertiary amines from the grouptetramethyl-ethylenediamine, pentamethylethylenetriamine,tetraethylethylenediamine, penta-ethylethylenetriamine and/ortributylamine or mixtures containing at least two of these amines.

In general, it is also possible to use a cyclic tertiary amine and/or anaromatic amino compound in the present process, as by reaction withN-alkylpyrrole, N-alkylpyrrolidine, N-alkylpiperidine,N-alkylmorpholine, N-alkylimidazole, N-alkylpiperazine, pyridine,pyrazine.

In a further alternative, the tertiary amine of formula II reacted inthe process of the present invention can be an aminoalkyl-functionalalkoxysilane having a radical of formula IIc or its hydrolysis and/orcondensation product; for example—but not exclusively—formula IIc orIIc* can correspond to a group B of formula III:

[(CH₃(CH₂)_(o)]₂N(R¹⁵)—  (IIc)

[(CH₃(CH₂)_(o)]₂N(CH₂)_(p)—  (IIc*),

where R¹⁵ is a linear, branched and/or cyclic alkylene, arylene oralkylenearyl group having 1 to 20 carbon atoms, where 0≦o≦6 and o isindependently=0, 1, 2, 3, 4, 5 or 6 in IIc and/or IIc*; moreparticularly R¹⁵ can be a —(CH₂)_(p)—, as depicted in formula IIc*, inwhich case 0≦p≦6 and p is independently=0, 1, 2, 3, 4, 5 or 6,and/or the tertiary amine of formula II can include a radical of formulaIId, more particularly formula IId or specifically formula IId* can be aradical of an aminoalkyl-functional alkoxysilane or its hydrolysisand/or condensation product; for example—but not exclusively—formula IIdor IId* can also correspond to a group B of formula III:

(R¹⁴)₂N[(CH₂)_(g)(NH)]_(s)—(R¹⁵)—  (IId)

(CH₃(CH₂)_(f))₂N[(CH₂)_(g)(NH)]_(s)—(CH₂)_(i)—  (IId*)

where R¹⁴ and R¹⁵ in IId are each independently defined as above andwhere, in formula IId and/or IId*, 0≦g≦6, 0≦s≦6, i.e., g and/or s areeach independently equal to 0, 1, 2, 3, 4, 5 or 6, and/or, in formulaIId*, R¹⁴ represents a (CH₃(CH₂)_(f)— group and R¹⁵ represents a—(CH₂)_(i)— group, with 0≦f≦3; 0≦g≦6, 0≦s≦6, 0≦i≦6, i.e., f=0, 1 or 2;g, s and/or i are each independently equal to 0, 1, 2, 3, 4, 5 or 6.

Examples of compounds of these tertiary silane-functionalized amines ofthe general formula II are depicted hereinbelow, wherein the radicals ofthe compounds are substituted as defined in IIc, IIc* and III:

([(CH₃(CH₂)_(o)]₂N(R¹⁵)—)_(1+b)Si(R⁸)_(a)(R⁷0)_(3-a-b)

((R¹⁴)₂N[(CH₂)_(g)(NH)]_(s)—(R¹⁵)—)_(1+b)Si(R⁸)_(a)(R⁷0)_(3-a-b)

where a is equal to 0, 1 or 2, b is equal to 0, 1 or 2 and (a+b)<3.

Additionally and/or alternatively, the tertiary amine can be anN-alkylpyrrolidine, N-arylpyrrolidine, N-alkylpiperidine,N-alkylmorpholine, N-alkylimidazolidine, N-alkylpiperazine,N,N′-dialkylpiperazine, acridine, phenazine, pyrazine.

Useable tertiary amines are advantageously trimethylamine, triethylamineand/or preferably at least one of the following amines selected fromtriisopropylamine, tri-n-propylamine, tribenzylamine,dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine,diethyl-n-octylamine, dimethyldodecylamine, dimethylpentadecylamine,diethyloctadecylamine, dimethylheptadecylamine, diethyltetradecylamine,dimethylhexacosylamine, methylethylisopropylamine,methylethylbenzylamine, diethyldecylamine, methyldipentylamine,kethylethylheptylamine, methylethylnonylamine, cyclopropyldimethylamine,cyclobutyldiethylamine, cyclopentyldi-n-propylamine,cyclohexyldimethylamine, cyclohexyldiethylamine,cyclohexylmethylethylamine, cycloheptyldimethylamine,cyclooctyldiethylamine, cyclohexyldioctylamine, cyclononyldimethylamine,cyclodecyldiethylamine, cycloundecyldimethylamine,cyclododecyldiethylamine, N-methylpyrrolidine, (=N-methylazolidine underIUPAC Rules), N-ethylpyrrolidine, N-isopropylpyrrolidine,N-benzyl-5-pyrrolidine, N-methylpiperidine, N-ethylpipericine,N-n/isopropylpiperidine, N-benzylpiperidine, N-methylmorpholine or4-methyltetrahydro-1,4-oxazine, N-ethylmorpholine, N-n-butylmorpholine,N-benzylmorpholine, N-methylimidazolidine, N-ethylimidazolidine,N-n-pentylimidazolidine, N-benzylimidazolidine, N-methylpiperazine,N-ethylpiperazine, N-isopropylpiperazine, N-benzylpiperazine,N-methylthiazolidine, N-ethylthiazolidine, N-methyloxazolidine,N-methyltetrahydro-1,4-thiazine, N-ethyltetrahydro-1,4-thiazine,N-benzyltetrahydro-1,4-thiazine, N-methylperhydroacepine,N-methylhexamethyleneimine, N-ethylperhydroacepine,N-benzylperhydroacepine, N-methylperhydrooxine(=N-methylheptamethyleneimine), N-isopropylperhydrooxine,N-benzylperhydrooxine, N-ethyltetramethyleneimine,N-methylpentamethyleneimine, N-ethylpentamethyleneimine andN-benzylpenta-methyleneimine.

By way of tertiary amines of formula II it is preferably also possibleto use the following amino-functional alkoxysilanes having tertiaryamino groups, such as, more particularly, tertiary aminoalkoxysilanes,diaminoalkoxysilanes, triaminoalkoxysilanes,bis(triethoxysilylalkyl)amine or tris(triethoxysilylalkyl)amine.

Possible bis(alkoxysilylalkyl)amine compounds include particularly(OR^(1**))_(b*)R²*_(a*)Si-A-SiR²*_(a*)(OR^(1**))_(b*), with a*, b*=0, 1,2 or 3 and a*+b* equal 3 per Si atom, where R^(1**) and R^(2*) are eachindependently alkyl having 1 to 24 carbon atoms, preferably methyl,ethyl and/or propyl. With A for a bisaminoalkyl-functional group offormula V, where N^(#) in V can correspond to the tertiary nitrogen (N)of formula V,

—(CH₂)_(i*)—[NR¹⁶(CH₂)_(f*)]_(g*)N^(#)R¹⁶[(CH₂)_(f*)NR¹⁶]_(g*)—(CH₂)_(i*)—  (V)

where R¹⁶ in each occurrence can be independently a branched, unbranchedand/or cyclic alkyl, aryl or alkylaryl group having 1 to 20 carbonatoms, where R¹⁶ is preferably methyl or ethyl, more preferably methyl,and where in formula V i*, f* or g* are each independently the same ordifferent, with i*=0 to 8, f*=1, 2 or 3, g*=0, 1 or 2 and R^(1**)corresponding to a linear, cyclic and/or branched alkyl radical having 1to 4 carbon atoms, where i* corresponds particularly to one of thenumbers 1, 2, 3 or 4, preferably 3, and[(H₅C₂O)₃Si(CH₂)₃NCH₃(CH₂)₃Si(OC₂H₅)₃ is particularly preferred.

Useful tris(alkoxysilylalkyl)amines, particularly of formula VI,include,

N[ZSi(R¹²)_(Ω)(OR¹³)_(3-Ω)]₃  (VI)

where Z in each occurrence is independently a bivalent alkylene radical,particularly from the series —CH₂—, —(CH₂)₂—, —(CH₂)₃— or—[CH₂CH(CH₃)CH₂]—, R¹² is a linear, branched and/or cyclic alkyl radicalhaving 1 to 24 carbon atoms, more particularly having 1 to 16 carbonatoms and preferably having 1 to 8 carbon atoms and more preferablyhaving 1 to 4 carbon atoms, or is an aryl radical and independently Q is=0 or 1, R¹³ in each occurrence is independently in VIII a linear,cyclic and/or branched alkyl radical having 1 to 24 carbon atoms, moreparticularly having 1 to 16 carbon atoms, preferably having 1 to 8carbon atoms, more preferably having 1 to 4 carbon atoms. Preferably,R¹³ is a methyl, ethyl or propyl radical. The nitrogen of formula VIIIagain corresponds to the nitrogen (N) of the more general formula V and[ZSi(R¹²)_(Ω)(OR¹³)_(3-Ω)] would correspond to an R¹. Preference for useas tertiary tris(trialkoxysilane)amine is given totris(triethoxysilylpropyl)amine or tris(trimethoxysilylpropyl)amine. Ingeneral, compounds of formula VI, the hydrolysis and/or condensationproducts thereof can be used as tertiary amine in the process of thepresent invention.

The process of the present invention more preferably utilizes ahaloalkyl-functional silane of formula I selected from the followinggroup: chloropropyltrimethoxysilane, chloropropyltriethoxysilane,chloropropylmethyldimethoxysilane and chloropropyl-methyldiethoxysilaneand/or its hydrolysis and/or condensation product.

Further haloalkylsilanes of formula I which are preferably useable inthe process of the present invention are, more particularly selectedfrom the group, 3-chloropropyltrimethoxysilane,3-chloropropyltriethoxysilane, 3-chloropropyl-tripropoxysilane,chloropropylmethyldimethoxysilane, chloropropylmethyl-diethoxysilane,chloropropyldimethylethoxysilane, chloropropyldimethylmethoxysilane,chloroethyltrimethoxysilane, chloroethyltriethoxysilane,chloroethylmethyl-dimethoxysilane, chloroethylmethyldiethoxysilane,chloroethyldimethylmethoxysilane, chloroethyldimethylethoxysilane,chloromethyltriethoxysilane, chloromethyl-trimethoxysilane,chloromethylmethyldimethoxysilane, chloromethylmethyl-diethoxysilane,chloromethyldimethylmethoxysilane, chloromethyldimethyl-ethoxysilane,2-chloroisopropyltris(methoxyethoxy)silane,3-chloropropylcyclo-hexyldiethoxysilane,3-chloroisobutyltrimethoxysilane, 3-chloroisobutyltriethoxysilane,3-chloropropylcyclohexyldimethoxysilane,3-bromoisopropyldiethylcyclohexoxysilane,3-chloropropylcyclopentyldieneethoxysilane,3-bromoisobutyltrimethoxysilane,3-chloroisobutylbis(ethoxyethoxy)methylsilane,4-bromo-n-butyltriethoxysilane,4-chloro-n-butyldiethoxycyclopentylsilane,5-chloro-n-pentyltri-n-butoxysilane, 5-bromo-n-pentyltriethoxysilane,4-bromo-3-methylbutyldimethoxyphenylsilane,5-bromo-n-pentyltri-n-butoxysilane, 5-chloro-n-pentyltriethoxysilane,6-chloro-n-hexylethoxydimethylsilane,6-bromo-n-hexylpropyldipropoxysilane,6-chloro-n-hexyldiethoxyethylsilane, 7-chloro-n-heptyltriethoxysilane,7-chloroheptyldimethoxy-cycloheptylsilane, 7-bromo-n-heptyl-,diethoxycyclooctylsilane, 8-chloro-n-octyltriethoxysilane,8-bromo-n-octyldimethylcyclohexoxysilane,3-chloropropyl-diethoxyphenylsilane,3-chloropropylmethoxyethoxybenzylsilane,3-bromopropyl-dimethoxybenzylsilane and/or their hydrolysis and/or homo-and/or co-condensation products or advantageously1,4-chlorophenyltrimethoxysilane, 1,4-chlorobenzyl-triethoxysilane andchloromethyl-p-methylphenyltrimethoxysilane and/or their hydrolysisand/or homo- and/or co-condensation products are used. Particularpreference is given to using purely chloroalkyl-substitutedalkoxysilanes in the process of the present invention.

In preferred processes, R³ in formula I is a linear, branched and/orcyclic alkylene having 1 to 18 carbon atoms, more particularly amethylene (—CH₂—), ethylene [—(CH₂)₂—], propylene [—(CH₂)₃—], butylene[—(CH₂)₄— or —(CH₂)CH(CH₃)(CH₂)—] and n=0 with Hal equal chlorine. It isparticularly preferable for the grouping —[(R³)_(n)CH₂Hal] to be achloromethylene, chloroethylene, 3-chloropropylene, 2-chloropropylene,2-chloroisopropylene, chlorobutylene, chloroisobutylene, chloropentyl,chlorohexyl, chlorocyclohexyl, chloroheptyl, chlorooctyl, chloro-n-octylor chlorocyclooctyl group. Conveniently, the correspondingbromine-substituted groups can also be used for Hal or a grouping—[(R²)_(n)CH₂L] with L as leaving group with a sulfonicester-substituted group (e.g., triflate) or nitric acid or sulfuricester-substituted groups.

In a particularly preferred process variant, the reaction takes place inthe presence of at least one further water-soluble,condensation-capable, organofunctional silicon compound, its hydrolysis,homo-, co-, block co-condensate or mixtures thereof, particularly toform oligomeric/polymeric quaternary aminoalkyl-functional organosiliconcompounds by condensation reactions.

This silicon compound, its hydrolysis, homo-, co-, block co-condensate,more particularly monomeric, oligomeric or polymeric silicon compounds,or mixtures thereof, are more particularly derived from at least onecompound of formula III and can be added to the process particularlytogether with a compound of formula I and/or II, as defined above, orafter at least single addition of water. The co-condensation of twoalkoxysilanes is thereafter shown in idealized form (the R groups may analkyl or aminoalkyl group, for example—but not exclusively—methyl,ethyl, propyl, butyl, N,N-dimethylaminoethyl):

Co-condensation:

NH₂(CH₂)₃—Si(OEt)₃+x Cl⁻(R)₃N⁺—(CH₂)₃—Si(OH)₃+3 H₂O->[(HO)₂Si(—(CH₂)₃NH₂—[O—Si(—(CH₂)₃—N⁺(R)₃)(OH)]_(x-1)—O—Si((—(CH₂)₃—N⁺(R)₃)(OH)₂].xCl⁻+(x+1)H₂O+3 EtOHand alsoF₃C(CF₂)₅(CH₂)₂—Si(OEt)₃+x Cl⁻(R)₃N⁺—(CH₂)₃—Si(OH)₃+3H₂O->[(HO)₂Si(—(CH₂)₂(CF₂)₅CF₃)—[O—Si(—(CH₂)₃—N⁺(R)₃)(OH)]_(x-1)—O—Si((—(CH₂)₃—N⁺(R)₃)(OH)₂].xCl⁻+(x+1)H₂O+3 EtOH

-   -   where the condensation/co-condensation can be continued and x        can be a number from 1 to ∞.

By way of oligomeric or polymeric silicon compounds there can be used inthe process of the present invention as they are for example but notexclusively disclosed, discernible or cited in WO 2006/010666, EP 0 846717 A1, EP 0846 716 A1, EP 1 101 787 A1, EP 0 960 921 A1, EP 0 716 127A1, EP 1 205 505 A, EP 0 518 056 A1, EP 0 814 110 A1, EP 1 205 481 A1and EP 0 675 128 A, the disclosure content of the preceding documentsbeing expressly incorporated herein in full by reference.

For this purpose, component C is suitably additionally used in theprocess of the present invention, particularly during the reaction, andcomprises at least one further organofunctionalized silicon compound offormula III, its hydrolysis products, condensation products or mixturesthereof,

(R⁷0)_(3-a-b)(R⁸)_(a)Si(B)_(1+b)  (III)

-   -   where R⁷ in each occurrence independently represents hydrogen, a        linear, branched and/or cyclic alkyl group having 1 to 8 carbon        atoms, aryl, arylalkyl or acyl, preferably alkyl having 1 to 5        carbon atoms, more preferably methyl, ethyl, propyl, R⁸ in each        occurrence independently signifies a linear, branched and/or        cyclic alkyl group having 1 to 24 carbon atoms, preferably        having 1 to 16 and more preferably having 1 to 8 carbon atoms;        aryl, arylalkyl and/or acyl and    -   the B groups are the same or different and B represents an        organofunctional group, a is equal to 0, 1 or 2, b is equal to        0, 1 or 2 and a+b<3,        in particular the compound of the formula III is selected from        compounds with    -   B being equal to —[(R¹0)_(n)R⁹], where R¹⁰ represents a linear,        branched and/or cyclic alkylene and/or alkenylene having 1 to 18        carbon atoms, n is equal to 0 or 1 and R⁹ in each occurrence        independently signifies a substituted or unsubstituted linear,        branched and/or cyclic alkyl group having 1 to 30 carbon atoms        which may optionally include one or more —NR^(3*) ₂, —OR^(3*)        and/or —SR^(3*) groups, with R^(3*) representing hydrogen and/or        with R^(3*) equal R⁹ and/or R⁹ together with a heteroatom N, S        or O being a cycle or heteroaromatic having 1 to 7 carbon atoms,    -   B being equal to (R^(5*)0)_(3-x*)(R^(6*))_(x*)Si((R^(2*))CH₂—),        where R^(5*) in each occurrence independently represents        hydrogen, a linear, branched and/or cyclic alkyl group having 1        to 8 carbon atoms or represents aryl, arylalkyl and/or acyl,        preferably alkyl having 1 to 5 carbon atoms, particularly        preferably methyl, ethyl, propyl, R^(6*) in each occurrence        independently signifies a linear, branched and/or cyclic alkyl        group having 1 to 24 carbon atoms, in particular having 1 to 16,        preferably having 1 to 8 carbon atoms, and/or aryl, arylalkyl        and/or acyl, R^(2*) is a linear, branched and/or cyclic alkylene        and/or alkenylene having 1 to 18 carbon atoms, preferably an        alkylene, and x* is equal to 0, 1 or 2,    -   B is a primary, secondary or tertiary amino-functional radical        of the general formulae IIIa or IIIb,

R¹¹_(h*)NH_((2-h*))[(CH₂)_(h)(NH)]_(j)[(CH₂)_(l)(NH)]_(c)—(CH₂)_(k)—  (IIIa)

where 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; c=0, 1 or 2; 0≦k≦6 andR¹¹ corresponds to a benzyl, aryl, vinyl, formyl radical and/or alinear, branched and/or cyclic alkyl radical having 1 to 8 carbon atoms,preferably k=3, c=1 or 2, l=1, 2 or 3 and j=0, more preferably k=3, c=1or 2, l=2 for a (2-aminoethylene)-3-aminopropyl radical, or j=0; c=2 andk=3, or else j=1; c=1 and k=3 with h=2, l=2 for atriaminoethylene-3-propyl radical; and in formula IIIb

[NH₂(CH₂)_(d)]₂N(CH₂)_(p)—  (IIIb)

0≦d≦6 and 0≦p≦6, preferably with d equal 1 or 2 and p equal 3,

-   -   B is equal to —(CH₂)_(i*)        —[NH(CH₂)_(f*)]_(g*)NH[(CH₂)_(f*)NH]_(g*)        —(CH₂)_(i*)—SiR²*_(a*)(OR^(1**))_(b*)(IIIc), where i*, f* or g*        in formula IIIc are each independently identical or different,        with i*=0 to 8, f*=1, 2 or 3, g*=0, 1 or 2 and R^(1**)        corresponding to a linear, cyclic and/or branched alkyl radical        having 1 to 4 carbon atoms, where i* is more particularly one of        the numbers 1, 2, 3 or 4, preferably 3, with a*, b*=0, 1, 2 or 3        and a*+b* equal 3 and R^(2*) an alkyl radical having 1 to 24        carbon atoms,    -   B is a radical R¹²—Y_(q)—(CH₂)_(s)—, where R¹² corresponds to a        mono-, oligo- or perfluorinated alkyl radical having 1 to 20        carbon atoms or to a mono-, oligo- or perfluorinated aryl        radical, where Y further corresponds to a —CH₂—, —O—, -aryl or        —S— radical and q is =0 or 1 and s is =0 or 2, more particularly        B corresponds to a perfluorinated alkyl radical having 1 to 20        carbon atoms,    -   B is a vinyl, allyl, isopropenyl radical, mercaptoalkyl radical,        sulfanealkyl radical, ureidoalkyl radical, acryloyloxyalkyl        radical, methacryloyloxyalkyl radical, or a linear, branched or        cyclic alkoxy radical having 1 to 24 carbon atoms, more        particularly having 1 to 16 carbon atoms and preferably having 1        to 4 carbon atoms, more particularly with a equal 0 and b equal        0, 1 or 2 in formula III for a tetraalkoxysilane,    -   B is a hydroxyalkyl, epoxy and/or ether radical, more        particularly a 3-glycidyloxyalkyl, 3-glycidyloxypropyl,        dihydroxyalkyl, epoxyalkyl, epoxycycloalkyl,        polyalkylglycolalkyl radical or a polyalkylglycol-3-propyl        radical, or    -   at least partial hydrolysis and condensation products of one or        at least two compounds of formula III.

Preferably, homo-, co- or else block co-condensates of at least twodifferent compounds of formula III can be used as oligomeric orpolymeric silicon compounds in the process, as known for example but notexclusively from WO 2006/010666, and also from the aforementioned EPdocuments.

Preferred compounds of formula III are:

-   bis(triethoxysilylpropyl)amine [(H₅C₂O)₃Si(CH₂)₃NH(CH₂)₃Si(OC₂H₅)₃,    bis-AMEO]. Further preferred compounds are:    (H₃CO)₃Si(CH₂)₃NH(CH₂)₃Si(OCH₃)₃ (bis-AMMO),    (H₃CO)₃Si(CH₂)₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃ (bis-DAMO),    (H₃CO)₃Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃ (bis-TRIAMO),    bis(diethoxy-methylsilylpropyl)amine,    bis(dimethoxymethylsilylpropyl)amine,    bis(triethoxysilyl-methyl)amine, bis(trimethoxysilylmethyl)amine,    bis(diethoxymethylsilylmethyl)amine,    bis(dimethoxymethylsilylmethyl)amine,-   (H₃CO)₂(CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₂(CH₃) and/or-   (H₃CO)₃(CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₂ (CH₃).

Preferred aminoalkyl-functional silanes of formula III are:

-   diaminoethylene-3-propyltrimethoxysilane    (H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, DAMO);-   triaminodiethylene-3-proplytrimethoxysilane    H₂N(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃ (TRIAMO),    (2-aminoethylamino)ethyltriethoxysilane, butyl    N-butyl-3-aminopropyl-triethoxysilane,    N-butyl-3-aminopropylmethyldiethoxysilane,    N-butyl-3-aminopropyl-trimethoxysilane,    N-butyl-3-aminopropylmethyldimethoxysilane,    N-butyl-1-amino-methyltriethoxysilane,    N-butyl-1-aminomethylmethyldimethoxysilane,    N-butyl-1-aminomethyltrimethoxysilane,    N-butyl-1-aminomethylmethyltriethoxysilane,    N-formyl-3-aminopropyltriethoxysilane,    N-formyl-3-aminopropyltrimethoxysilane,    N-formyl-1-aminomethylmethyldimethoxysilane and/or    N-formyl-1-aminomethylmethyldiethoxy-silane, and also the    corresponding N-methyl-, N-ethyl-, N-propyl-substituted aminosilanes    or mixtures thereof. By way of amino-functionalized silicon    compounds there can be used in particular the following, such as    bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine,    3-aminopropylmethyldiethoxysilane,    3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane,    aminoethyl-N′-2-aminoethyl-N-3-aminopropyltrimethoxysilane,    N-(n-butyl)-3-aminopropyltrimethoxysilane,    benzyl-2-aminoethyl-3-aminopropyltrimethoxysilane,    2-aminoethyl-3-aminopropylmethyldimethoxysilane,    2-aminoethyl-3-aminopropyltrimethoxysilane, and/or their hydrolysis,    homo- and/or co-condensation products and/or mixtures thereof.

By way of organo-functionalized silicon compounds as per component Cthere can also be used particularly the following, such asphenyltrimethoxysilane, phenyltriethoxysilane,3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,tridecafluoroctyltriethoxysilane, ethyl polysilicate, tetraethylorthosilicate, tetra-n-propyl orthosilicate,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane,3-ureidopropyltrimethoxysilane, vinyltriethoxysilane,vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane,vinylbenzyl-2-aminoethyl-3-aminopropylpolysiloxane optionally inmethanol and/or their hydrolysis, homo- and/or co-condensation productsand/or mixtures thereof.

It can further be preferable to use metal oxides as further component inthe process of the present invention, preferably metal oxides havingcondensation-capable hydroxyl groups. These are more particularlysilica, pyrogenous silicic acid, precipitated silicic acid, silicates,boric acid, titanium dioxide, aluminum oxide, aluminum oxide hydrate,ATH (aluminum trihydroxide, Al(OH)₃), magnesium hydroxide (Mg(OH)₂),cerium oxide, yttrium oxide, calcium oxide, iron oxide, zirconium oxide,hafnium oxide, boron oxide, gallium oxide, indium oxide, tin oxide,germanium oxide and also corresponding hydroxides and oxide hydrates andalso mixtures of at least two of the aforementioned compounds with oneanother.

To adjust the pH and/or as catalyst, the composition or reaction mixturemay have added to it at all times an organic or inorganic acid, forexample formic acid, acetic acid, hydrochloric acid or other acidsfamiliar to a person skilled in the art.

It is particularly preferable for the following compounds of formula I,II and of formula III, their hydrolysis and/or condensation products ormixtures thereof to be used and reacted in the inventive process forpreparing inventive quaternary amino-functional organosilicon compounds,such as preferably: formula I and II with formula III where the B groupcorresponds to a radical —[(R¹⁰)_(n)R⁹]_(1+b); formula I and II with twocompounds of formula III with group B equal —[(R¹⁰)_(n)R⁹]_(1+b), and afurther compound of formula III with group B wherein group B correspondsto a primary, secondary and/or tertiary amino-functional group of thegeneral formulae IIIa or IIIb; formula I and II with a compound offormula III where group B corresponds to a radical R¹²—Y_(q)—(CH₂)_(s)—;formula I and II with two different compounds of formula III where one Bgroup corresponds to a radical R¹²—Y_(q)—(CH₂)_(s)— and another B groupcorresponds to a primary, secondary and/or tertiary amino-functionalgroup, more particularly of the general formulae IIIa or IIIb; formula Iand II with a compound of formula III wherein group B corresponds to ahydroxyalkyl, epoxy radical, more particularly a 3-glycidyloxyalkyl,3-glycidyloxypropyl, dihydroxyalkyl, epoxyalkyl, epoxycycloalkylradical; formula I and II with a tetraalkoxysilane of formula III.

In the process of the present invention, the silane(s) of formula IIIand/or hydrolysis, homo- and/or co-condensation products thereof can beinitially charged together with the chloro-functionalized silane at thestart of the process, or be added to a reaction mixture of components Aand B at any later time in the course of the process. The addition canpreferably take place after the first, second or third addition ofwater.

More particularly, the process of the present invention can be carriedout without use of iodides and substantially without any use ofsolvents, such as glycols or glycol ethers, i.e., substantially withoutaddition of a solvent. Moreover, it is particularly the aqueouspreparation of the organosilicon compounds which forecloses theadditional use of hydrosilanes in the process of the present invention.

The process can be carried out with advantage as follows. First, thehaloalkyl-functional silane, more particularly a component A, andoptionally at least one silane of formula III, i.e., optional componentC, are mixed in a suitable reaction vessel; for example a stirred tankreactor with temperature control, metering means and distillationapparatus; with the tertiary amine, more particularly a component B. Thetemperature here should be below the boiling temperature of the amineused and also below the boiling temperature of the silane usedrespectively. Preferably, the silane or silane mixture is initiallycharged and the tertiary amine is rapidly added within a few seconds tominutes. The molar ratio of chloroalkyl function/tertiary aminofunctions of the compounds can vary in the range from 2:1 to 1:10. Whenthe ratio is 1:1, every chloroalkyl function will react with an aminofunction. Preferably, the ratio of all amino functions (primary,secondary and tertiary) to the chloroalkyl is about 1:1. When a lowerratio than 1:1 is chosen, unreacted amino functions remain in thecomposition, which remain in the solution or can be separated off. Whenthe tertiary amine contains more than one tertiary amino function, aratio lower than 1:1 for tertiary amine to chloroalkyl function can beused in order that all the tertiary amines may be allowed to react witha chloroalkyl function.

In addition, a preferred embodiment of the process of the presentinvention can be carried out with advantage when

-   -   the components A and B and optionally C are mixed, wherein the        mixture may optionally have added to it a diluent medium,        preferably an alcohol, more preferably methanol, ethanol,        isopropanol,    -   water is continuously or discontinuously metered into the        mixture in an amount of 0.5 to 500 mol of water per mole of        silicon atoms present, preferably under stirring, and optionally        a catalyst is added to the reaction mixture,    -   the reaction mixture present is set to a temperature between 20        and 150° C. at ambient pressure or reduced pressure, and    -   the resultant hydrolysis alcohol is at least partially,        preferably essentially completely, removed from the reaction        mixture as is any solvent/diluent medium used, and    -   the composition thus obtained is optionally diluted with water,        wherein the level of active ingredient, i.e., of mixture of        quaternary amino-functional organosilicon compounds which is        obtained according to the process and which contains at least        one oligomerized quaternary amino-functional organosilicon        compound, in the composition is preferably adjusted to 0.1% to        99.9% by weight and thereafter optionally admixed or contacted        with at least one further component from the series of pigments,        fillers, binders, crosslinkers, optical brighteners, thickeners,        rheological auxiliaries, coating auxiliaries or some other        auxiliary.

When 3-chloropropyltriethoxysilane (CPTEO) is reacted withtetramethylethylene-diamine (TMEDA), for example, a ratio of about 1:2for chloroalkyl functions to tertiary amine functions can be sufficientto achieve full reaction of practically all TMEDA molecules, seeexample 1. A ratio of >1:1 for the functional groups will leave behindunreacted chloroalkylsilyl functions which, however, can beco-incorporated in the oligomeric end product through hydrolysis of thealkoxysilyl functions and condensation of the silanol functions. Whenfurther organofunctional alkoxysilanes are used during hydrolysis andcondensation reaction, as per formula III, they will becomeco-incorporated into the inventive oligomeric product, see in theidealized form formula VII.

This makes it possible to obtain inventive multifunctional oligomeric orpolymeric quaternary aminoalkyl-functional organosilicon compounds offormula VII which, in addition to the quaternary amino function, containfurther organofunctional groups.

The use, for instance, of alkylalkoxysilanes, e.g., methyl-, propyl-,butyl-, isobutyl-, octyl-, isooctyl- or hexadecyltrialkoxysilanes or-methyldiethoxysilanes or -dimethylalkoxysilanes, can result in theformation of alkylsilyl- and quaternary amino-functional co-condensates.In the same way it can also be used to introduce further organofunctions, for example amino, diamino, triamino, mercapto, glycidyloxy,(meth)acryloxy or fluoroalkyl functions, into the oligomeric product.

Diluents, including for example methanol or ethanol, can be used inspecial cases to adjust the viscosity for example. Preferably, nosolvent is used. A diluent can also be used in the subsequent steps,hydrolysis and/or condensation and more particularly distillation forviscosity adjustment and for solubilization. In the course of thedistillation step, the diluent is removed again according to the presentinvention.

The mixing operation is preferably carried out as rapidly as possible.This is followed by the addition of water, particularly in an amountbetween 0.5 mol of water per mol of Si to 500 mol of water per mol ofSi. The water is added under agitation within a period between 1 min and10 hours, preferably within 10 min to 1 hour. The reactionmixture/solution usually becomes cloudy in the process. It is stirredand heated, particularly between 10° C. to the reflux temperature,depending on the inputs used, the reaction is preferably carried out at20 to 150° C. and more preferably below 100° C., until a clear solutionhas formed.

It is preferable to maintain a postreaction period under reflux,particularly in the aforementioned temperature range, of 30 minutes to24 h and preferably between 1 h to 8 h. Further water can be addedduring this period. This is followed by distillative removal ofhydrolysis alcohols and any solvents added. The distillatively removedamount is preferably replaced with equal parts of water. This can bedone by continuous addition or by addition in sub-steps. It ispreferable for the addition to take place in sub-steps wherein the rateof addition is preferably set as high as possible.

The distillation preferably takes place under reduced pressure, moreparticularly between 0.01 mbar to 1000 mbar, more particularly between 1to 1000 mbar and more preferably between 80 to 300 mbar. Distillation ispreferably carried on until only water is detectable at the top of theseparation column. Distillatively removed water is replenished byrenewed addition of water. At the end of the distillation, the desiredfinal concentration for the solution can be set by adding further water.

The present invention accordingly also provides oligomeric/polymericquaternary aminoalkyl-functional organosilicon compounds and also theirmixtures obtainable by the process of the present invention.

The present invention further provides a composition containingquaternary aminoalkyl-functional organosilicon compounds and water,obtainable by the process of the present invention.

The level of inventively quaternary amino-functional organosiliconcompound, more particularly of formula VII, in subject compositions canbe set as desired in a range between 0.001% to 99.5% by weight andpreferably between 0.1% by weight to 90% by weight, in the overallcomposition.

Compositions according to the present invention are preferably marked bya content of active ingredient, i.e., quaternary amino-functionalorganosilicon compounds obtained according to the process, thecomposition containing at least one oligomerized quaternaryamino-functional organosilicon compound, in the composition ranging from0.1% to 99.9% by weight, preferably 0.5% to 90% by weight, morepreferably 5% to 70% by weight, even more preferably 7% to 60% by weightand more particularly 10% to 50% by weight, wherein all the constituentsin the composition sum to 100% by weight.

Compositions according to the present invention are further marked by awater content in the range from 0.0999 to 99.9% by weight, and areadvantageously thinnable with water in practically any proportion: thesecan also have a level of volatile solvent/hydrolysis alcohol in theoverall composition of below 12% by weight to 0% by weight, preferablybelow 5% to 0.0001% by weight, wherein all the constituents in thecomposition sum to 100% by weight.

The VOC content of the composition, as defined above, is thusadvantageously less than 12% by weight in the overall composition andmore preferably below 2% to 0% by weight.

In addition, compositions according to the present invention may containat least one further of the following components from the seriespigments, fillers, binders, crosslinkers, optical brighteners, coatingauxiliaries or other auxiliaries.

Compositions according to the present invention also advantageously havea viscosity of <1500 mPa s, preferably ≦1000 mPa s and more preferably10 to 600 mPa s, more particularly of 100 to 300 mPa s.

The end product obtained according to the present invention, or thecomposition according to the present invention, is generally liquid andminimally to slightly viscose in that the viscosity is more particularlybelow 1500 mPa s to 0.001 mPa s, preferably between 1000 and 1 mPa s,more preferably below 300 mPa s, even more preferably below 200 mPa s,yet even more preferably below 100 mPa s, still yet even more preferablybetween 100 mPa s and 1 mPa s, preference being further given to rangesfrom 200 to 1 mPa s and more particularly from 100 to 10 mPa s (theviscosity is determined in accordance with DIN 53015).

Moreover, a composition or silane product solution obtained according tothe present invention can be as required filtered in a conventionalmanner in the event of cloudiness.

A preferred use for the compositions of the present invention is theproduction of papercoating slips. For this it is suitable for an aqueoussilica dispersion to be prepared first and treated with the silanesystem of the present invention, usually under high shearing forcesapplied using dispersing equipment customary in the industry. Thesilanized silica dispersion obtained is advantageously marked by a highsolids content, high storage stability and low sedimentation tendency.Preferably, the silanized silica dispersion has binder, preferablypolyvinyl alcohol, and crosslinker, preferably boric acid, added to itin a second step to produce the papercoating slip, which is very usefulfor producing photographic grade inkjet papers.

Particular preference is given to a papercoating slip viscosity ofpreferably below 600 mPa s, more preferably below 450 mPa s, even morepreferably below 200 mPa s and more particularly in the range from 2 to150 mPa s, as in the case of the conditions chosen in example 9. Thelower the solids content of the formulation, the lower the capacity ofthe coating rigs operated therewith, since the volatile constituents ofthe papercoating slips (mainly water here) generally have to be removedthermally. The higher the solids content of the formulation, the lowerthe amount of water which has to be removed and the higher the rate ofspeed at which the coating rigs can be operated. A solids contentof >15% by weight is desired for papercoating slips under the conditionschosen in example 9.

Before use, the compositions according to the present invention and alsothe end products according to the present invention can if required beadvantageously thinned with water or other solvents or else mixturesthereof to a content between 10% to 0.01% by weight and preferably to arange from 5% to 0.1% by weight.

Thus, in addition to water, a composition according to the presentinvention may contain a quaternary aminoalkyl-functional organosiliconcompound of formula VII or mixtures thereof, more particularlyoligomeric or polymeric and optionally monomeric compounds of formulaVII or mixtures thereof,

R^(1*)N(R*)₃ ⁺Z⁻  (VII)

where R^(1*) and R* each independently correspond to identical ordifferent organofunctional groups, optionally two R* radicals combinewith N to form a cycle which are connected via a carbon atom to thequaternary nitrogen (N), and at least R^(1*), optionally also R*,comprises an Si atom; preferably the R* and/or R^(1*) radicalsindependently comprise a —CH₂—Si group; wherein the nitrogen is a cationand Z is an anion; more particularly formula VII is a quaternaryalkylammonium-functional organosilicon compound, more particularly Z isa chloride, bromide, acetate, formate, and preferably R^(1*) in formulaVII is a (R¹O)_(3-x-y)(R²)_(n)Si[(R³)_(n)CH₂— radical, with R¹ hydrogenand/or R^(1*) a hydrolysis or oligomeric or polymeric condensationproduct of this silyl radical.

According to the present invention, the subject composition isessentially free of volatile solvents, preferably of hydrolysis alcohol,and no longer releases any hydrolysis alcohol at crosslinking inparticular.

The present invention also provides an aqueous composition comprisingquaternary aminoalkyl-functional organosilicon compounds according tothe present invention, obtainable according to at least one of claims 1to 15. It is particularly preferable for the composition containingquaternary aminoalkyl-functional organosilicon compounds to beobtainable according to a process of claims 1 to 15 by reacting thecompounds of formulae I and II, as defined above, optionally in thepresence of at least one compound of formula III, as defined above,hydrolysis, condensation products or mixtures thereof, in the presenceof 0.5 to 500 mol of water and distillative removal of at least some ofthe hydrolysis alcohol. Preferably, the composition of the presentinvention is essentially free of organic solvents and releasesessentially no alcohol at crosslinking, and more particularly it has aflashpoint above 90° C.

The invention likewise provides a composition containing quaternaryaminoalkyl-functional organosilicon compounds and water, wherein thecomposition contains quaternary aminoalkyl-functional organosiliconoligomeric and polymeric and optionally monomeric compounds having atleast one quaternary aminoalkyl-functional group of the general formulaVII or mixtures thereof,

[R^(1*)N(R*)₃]⁺Z⁻  (VII)

where R^(1*) and R* each independently correspond to identical ordifferent organofunctional groups, optionally two R* radicals combinewith N to form a cycle which are connected via a carbon atom to thequaternary nitrogen (N), and at least R^(1*), optionally also R*,comprises an Si atom; preferably the R* and/or R^(1*) radicalsindependently comprise a —CH₂—Si group; wherein the nitrogen is a cationand Z is an anion; more particularly formula VII is a quaternaryalkylammonium-functional organosilicon compound, more particularly Z isa chloride, bromide, acetate, formate, and preferably R^(1*) in formulaVII is a (R¹O)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂— radical, with R¹ hydrogenand/or R^(1*) a hydrolysis or oligomeric or polymeric condensationproduct of this radical;and wherein the quaternary aminoalkyl-functional organosilicon compoundsof formula VII or mixtures thereof are obtainable from a quaternizationreaction and optionally at least partial hydrolysis and/or condensation

-   -   of at least one haloalkyl-functional silane of formula I and        optionally its hydrolysis and/or condensation products

(R¹O)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (I)

-   -   -   where R³ corresponds to a linear, branched and/or cyclic            alkylene and/or alkenylene having 1 to 18 carbon atoms,            preferably an alkylene, n is 0 or 1, Hal is chlorine or            bromine, preferably chlorine, R¹ in each occurrence is            independently hydrogen, a linear, branched and/or cyclic            alkyl group having 1 to 8 carbon atoms, aryl, arylalkyl            and/or acyl, more preferably alkyl having 1 to 5 carbon            atoms, preferably methyl, ethyl, propyl and R² in each            occurrence is independently a linear, branched and/or cyclic            alkyl group having 1 to 24 carbon atoms, more particularly            having 1 to 16 carbon atoms and preferably having 1 to 8            carbon atoms, or aryl, arylalkyl and/or acyl, x is 0, 1 or            2, y is 0, 1 or 2 and x+y is <3,        -   with a tertiary amine of the general formula II,

N(R⁴)₃  (II)

-   -   -   where R⁴ independently corresponds to organofunctional            groups which are connected by a C atom to the tertiary            nitrogen (N), optionally two R⁴ radicals combine with N to            form a cycle, more particularly R⁴ is a linear, branched            and/or cyclic substituted or unsubstituted alkyl group            having 1 to 30 carbon atoms optionally with one or more —NR⁵            ₂, —OR¹ and/or —SR⁶ groups, with R⁶ in each occurrence            independently hydrogen or R⁴; and/or one, two or three R⁴            radicals correspond to (R¹0)_(3-x)(R²)_(x)Si((R³)_(n)CH₂—)            and optionally its hydrolysis and/or condensation product,

    -   in the presence of a defined amount of water, optionally in the        presence of a catalyst, followed by an at least partial removal        of the hydrolysis alcohol formed and further addition of water.

The defined amount of water added is preferably in the range from 0.5 to500 mol of water per mol of silicon atoms, more particularly in therange from 5 to 25 mol of water per mol of silicon atoms, preferably inthe range from 10 to 20 mol of water per mol of silicon atoms and morepreferably in the range from 12 to 17 mol of water per mol of siliconatoms.

In idealized form, the quaternization reaction and partial hydrolysismay give rise to for example the following compound of formula VII:

or with formation of a quaternary nitrogen atom at the positioncharacterized with an (N*) and/or preferably corresponding hydrolysisand also condensation products (cf. formulae VIIc and VIId).

Here x can formally be a number from 1 to ∞ provided H₂O is completelyremoved from the system.

Moreover, in accordance with chemical understanding, compounds offormulae I and IIb may further give rise to compounds within the meaningof the idealized formula VII:

It is particularly preferable here for the hydrolysis alcohol to beremoved essentially completely, more particularly by distillationoptionally under reduced pressure. A composition deemed essentially freeof volatile solvent, more particularly hydrolysis alcohol, has a solventcontent below 12% by weight to 0% by weight in the overall composition,preferably below 12% to 0.0001% by weight, more particularly below 10%by weight to 0% by weight, more preferably below 5% by weight to 0% byweight, even more preferably between 2% to 0% by weight, preferablybetween 1% to 0% by weight and more preferably between 0.5% to 0.001% byweight.

Preferred compositions are obtainable by adding at least oneorganofunctional silicon compound of formula III, as defined above,hydrolysis or condensation products or mixtures thereof, before, duringor after the reaction of compounds of formula I and II. Theorganofunctional silicon compounds which can be used are described indetail above.

Preferably, the composition of the present invention is essentially freeof organic solvents and releases essentially no alcohol at crosslinking,and more particularly it has a flashpoint above 90° C.

Furthermore, the compositions obtainable by the process of the presentinvention have a viscosity of below 1500 mPa s to 0.001 mPa s, moreparticularly below 300 mPa s, preferably below 100 mPa s, morepreferably between 1000 and 1 mPa s. Preferred ranges are 200 to 100 mPas, 100 to 0.01 mPa s, 100 to 20 mPa s or else 10 to 20 mPa s, althoughwhich is the preferred range in a particular instance depends on thespecific use.

In an aqueous composition according to the present invention, thecontent, more particularly solids content, of quaternaryaminoalkyl-functional organosilicon compounds or a mixture thereof canadvantageously be from 0.001% to around 99.5% by weight (including allnumerical values therebetween), based on the overall composition. Thecontent can be set directly in the process of the present invention orelse be thinned by the user, for example with water, to any desiredconcentration, for example to from 0.0001% to 2% by weight in thecomposition. Specifically preferred contents of the compounds, such asthe solids content, are more particularly between 0.1% to 90% by weight,preferably 5% to 70% by weight, more preferably 10% to 50% by weight, orpreferably between 40% to 65% by weight. The compositions of the presentinvention are advantageously marked by a low viscosity coupled with asimultaneously high solids content, as evidenced by the exemplaryembodiments. This combination of low viscosity and high solids contentis a necessary prerequisite for a high capacity in the production ofcoatings. At the same time, the compositions of the present inventionare essentially VOC-free, i.e., they are essentially free of hydrolysisalcohol and release no alcohol at crosslinking. Thus, the compositionsof the present invention have a distinctly better performance than knowncompositions.

The claimed compositions are essentially stable in storage. That is,they do not exhibit any visible changes such as cloudiness orsedimentation or gelling within two weeks, preferably 3 months, morepreferably 1 year.

The invention also provides a formulation comprising a compositionaccording to the present invention which comprises at least one of thefollowing components from the series pigments, binders, crosslinkers,optical brighteners, coating auxiliaries, active ingredient and/orauxiliary and/or filler.

The compositions of the present invention are also very useful in inkjetcoatings, more particularly for high gloss coats on paper.

A detailed description of this use is given in the cocurrent inventionreport “Hydrosils with quaternary aminofunction for silica dispersionsin IJP application”. The production of papercoating slips based on acomposition according to the present invention is described in example9d.

The composition according to the present invention may be used byapplying it to a substrate by dipping, spreading, rubbing, spraying,more particularly with droplet sizes below 200 μm, preferably below 100μm down into the nanometer range; depositing, spincoating or any othertechnique known to a person skilled in the art. To this end, thecomposition is adjusted to an organosilicon compound concentrationsuitable for the method used. Depending on the processing method,therefore, the concentration of organosilicon compound in thecomposition can be in the range from 0.01% by weight to 99.5% by weight.The methods of application are well known to a person skilled in thepertinent art. In addition, a coating applied to a substrate cancure/bind to the substrate in a conventional manner under ambientconditions and/or via an additionally thermal and/or photochemicaltreatment. In this way, a composition according to the present inventioncan be used to treat organic or inorganic substrates, or as an inputcomponent in formulations, for example.

Inventive compositions or formulations which are based on an inventivecomposition are advantageously used for modification, treatment and/orproduction of substrates, articles, organic or inorganic materials,composite materials, papercoating slips, inkjet applications,papercoating materials, textiles, fillers; in biocidally,antibacterially, fungicidally, algicidally and/or virucidally actingformulations and/or coatings, for finishing of fiber materials, yarnsand/or textiles, for textile impregnation, for antistatisization ofsurfaces, more particularly sheetlike, fibrous, woven, granular and/orpulverulent materials, e.g., wood surfaces, mineral surfaces, glasssurfaces, ceramic surfaces, metal surfaces, plastics surfaces, porousmineral building materials, fiber materials, for example textile fibers;or for anti-fingerprint or anticorrosion coating of materials and metalsand also pretreated metals. Further fields of use comprise an antistaticfinishing of surfaces, e.g., of plastics, glass, ceramic, wood,lacquered surfaces, fiber materials such as glass fibers, mineral wool,carbon fibers, ceramic fibers or textile fibers (inc. fabrics producedfrom these fibers) and also mineral fillers for example silica,precipitated silicic acid, pyrogenous silicic acid, quartz, calciumcarbonate, gypsum, ATH, alpha and gamma Al₂O₃, magnesiumhydroxide/oxide, iron oxides, clay minerals, sheet-silicates or furtherfillers familiar to a person skilled in the art.

The products of the present invention can further be used formodification of fillers optionally in combination with otherorganofunctional silanes or hydrosilane, for example in order that abetter dispersibility may be achieved.

Particular preference is given to the use of a composition inpapercoating slips, more particularly for inkjet applications, forproduction of papercoating materials, as papercoating materials, forfinishing of fiber materials and/or textiles, for textile impregnationor for modification of fillers. Further preferred use is the coating offilters, tubes, fittings, medical devices or instruments, in swimmingpool paints, for coating tiles or surfaces which are in constant contactwith moisture or water, as in swimming pools, baths, bathroom ceramics,kitchen ceramics, an exterior skin of buildings, such as exteriors, roofcoverings, garden furniture, accessories in the marine sector, ropes,sail cloth, ship exterior skin, etc. and also further applications knownto the skilled person pertinent here where problems are known to occurwith microorganisms, or else of glass, windows, autoglass, mirrors,optical glasses, surgical instruments, or constituent parts of surgicalinstruments and microinvasive surgical instruments, endoscopes or partsthereof, canulas, medical hoses, medical apparatus and/or parts thereof,implants, prostheses, stents, gravestones, or of fibers, such as naturalfibers and/or artificial fibers, such as, more particularly, cotton,hemp, wool, silk, polyester, acetates, and further materials familiar tothe pertinent skilled person. Particular preference is given to the usein wound coverings or else hygiene articles, such as plasters, gauzedressings, diapers, pads and also further medical or hygiene articlesfamiliar to the pertinent skilled person. The coating here can range insize from large areas down into the micro- to nanometer region.

The present invention thus likewise further provides for the use of acomposition produced/obtainable according to the present invention formodification, treatment and/or production of formulations, substrates,articles, organic or inorganic materials, composite materials,papercoating slips, inkjet applications, papercoating materials,textiles, fillers, biocidally, fungicidally and/or virucidally actingformulations, for finishing of fiber materials, yarns and/or textiles,for textile impregnation, for antistatisization of surfaces, moreparticularly sheetlike, fibrous, woven, granular and/or pulverulentmaterials.

The examples which follow more particularly elucidate the presentinvention, more particularly the process of the present invention andalso the compositions of the present invention, without restricting theinvention to these examples.

EXAMPLES Methods of Determination

Hydrolyzable chloride was titrated potentiographically with silvernitrate (for example Metrohm, type 682 silver rod as indicator electrodeand Ag/AgCl reference electrode or another suitable referenceelectrode). Total chloride content after Wurtzschmitt digestion. Forthis purpose, the sample is digested with sodium peroxide in aWurtzschmitt bomb. After acidification with nitric acid, chloride ismeasured potentiographically with silver nitrate, as above.

In a complete reaction of the chloroalkyl function with tertiary amines,the analytical values for hydrolyzable chloride and total chloride areidentical and therefore a measure of the completeness of the reaction,since the sum total of salt-like chloride (amine hydrochloride) andcovalently bonded chlorine (chloroalkyl function) is determined by totalchloride and exclusively salt like chloride or chloride which can beeliminated with water (amine hydrochloride in the present case) isdetermined by hydrolyzable chloride. At the beginning of the reaction,the value of hydrolyzable chloride is zero and increases at completeconversion to the value which is measured for total chloride. Therefore,these analyses are very useful in addition to ¹H and ¹³C NMRspectroscopy for reaction policing.

The alcohol content after hydrolysis is determined by gaschromatography. For this purpose, a sample of a defined quantity ishydrolyzed with sulfuric acid (5 g of sample, 25 ml of H₂SO₄, w=20%). 75ml of distilled water are added. Thereafter, neutralization is effectedwith aqueous sodium hydroxide solution and a steam distillation iscarried out. Internal standard 2-butanol. Nitrogen determination,organically bound, ammonium etc. Organically bound nitrogen can beconverted into ammonium via Kjeldahl digestion and, after addition ofaqueous sodium hydroxide solution, be determined acidimetrically asammonia (see also DIN 1310, DIN 32625, DIN 32630, DIN EN 25663-H11, DIN38409-H12, AN-GAA 0629—Büchi 322/343). Determination of SiO₂ is doneafter decomposition with sulfuric acid and Kjeldahl catalyst bydetermining the weight of precipitated SiO₂.

The viscosity is generally determined to DIN 53015.

The determination of the solids content, i.e., of the nonvolatilefractions in aqueous and solvent-containing preparations, can be carriedout in line with DIN/EN ISO 3251 (Determination of theNon-Volatile-Matter Content of Paints, Varnishes and Binders for Paintsand Varnishes) as follows (QM-AA Quality Management OperatingInstruction as per German Accreditation Body for Chemistry):

-   Test instruments—Thermometer (reading accuracy 2 K)    -   Disposable dishes of aluminum (d=ca. 65 mm, h=ca. 17 mm)    -   Analytical balance (accuracy 1 mg)    -   Drying cabinet to 250° C.    -   Desiccator

A sample is heated to a specified temperature (e.g., 125° C.) in orderto remove the volatile fractions of the sample in this way. The solidscontent is the dry residue of the sample after the heat treatment.

About 1 g of sample is weighed with an accuracy of 1 mg into adisposable dish on an analytical balance. The product must be uniformlydistributed in the disposable dish by brief swirling. The dish is storedin a drying cabinet at about 125° C. for 1 h. On completion of thedrying operation, the dish is cooled down to room temperature in adesiccator for 20 min and reweighed on the analytical balance accuratelyto 1 mg. At least 2 determinations must be carried out per test.

${{Solids}\mspace{14mu} {{content}(\%)}} = {\frac{{final}\mspace{14mu} {{weight}(g)}}{{Original}\mspace{14mu} {{weight}(g)}} \times 100}$

-   Solids content —Percentage ratio of sample mass before and after    treatment.-   Final weight—The sample mass after treatment.-   Original weight—The sample mass before treatment.

Example 1

Waterborne VOC-free solution of a quaternary silane system prepared from3-chloropropyltriethoxysilane (CPTEO) and tetramethylethylenediamine(TMEDA).

Apparatus: stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

M N w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyltriethoxysilane 3206.2 13.31 37.3 M = 240.8 g/ mol N,N,N′N′-1547.2 13.31 18.0 M = 116.21 g/ tetramethylethylenediamine molCompletely ion-free water: 1st addition 1603.1 18.6 2nd addition 641.37.5 3rd addition 1600.0 18.6 Σ (inputs) 8597.8 m (ethanol ex hydrolysis)= 1836.8 g; final weight of product after filtration: 6521.4 g (theory:6761.1 g); final weight of distillate: 2946.5 g

Procedure:

-   1. Reaction (duration about 9.7 h): Chloropropyltriethoxysilane is    initially charged and tetramethylethylenediamine is rapidly added    with stirring. This is followed by the 1st addition of water within    about 20 minutes (volume stream about 4.8 l/h) under vigorous    stirring. The pot contents are distinctly cloudy and then heated    under reflux (about 87° C.) for 6 h. The 2nd addition of water is    then made during 10 minutes into the now clarified pot contents    (volume stream about 3.9 l/h). After a further 1.5 h of heating    under reflux, the 3rd addition of water is made with stirring    (during about 20 minutes, volume stream about 4.8 l/h).-   2. Distillation (duration about 9 h): At a pot temperature of 49° C.    to 54° C., hydrolysis ethanol is distilled off under reduced    pressure (100-270 mbar). After about 1700 g of ethanol-water mixture    have been distilled off, 327 g of water are rapidly added. To    distill off the hydrolysis alcohol almost completely, an at least    60% excess (based on the mass of hydrolysis ethanol) has to be    distilled off. The distillatively removed amount of water is    returned at the end of the distillation.-   3. Filtration (duration about 1 h): Thereafter, the slightly cloudy    yellowish product is filtered via pressure filter (2 l) and Seitz    500 depth filter at 0.8 bar overpressure (filtration performance at    d_(filter)=14 cm: 18 l/h). A slightly yellowish clear liquid is    obtained.

Analyses:

Determination Result Theory Method Viscosity (20° C.) 70 DIN 53015 [mPas] Density (20° C.) 1.107 DIN 51757 [g/ml] Refractive index 1.4224 DIN51423 (20° C.) Color [mg Pt—Co/l] 75 Solids [%] 48.4 DIN 38409-1 pH 8.61:1 in water, DIN 38404-C5 SiO₂ [%] 11.8 11.8 see above Ethanol after0.5 see above hydrolysis [%] Total N [%] 5.0 5.5 see above Totalchloride [%] 7.2 7.0 see above Hydrol. chloride [%] 7.1 7.0 see aboveNMR: ¹³C-NMR: about 15% of TMEDA groups are in bisadduct form. 8 mol %of free TMEDA is present per 100 SiCH₂ groups. ²⁹Si-NMR: 2.5 Si % ofsilane; 14.6 Si % of M-structures; 49.7 Si % of D-structures; 33.3 Si %of T-structures

Example 2

Waterborne VOC-free solution of a quaternary silane system prepared from3-chloropropyltriethoxysilane and tetramethylethylenediamine with excessof tetramethylethylenediamine

Apparatus: stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyl- 401.19 1.67 36.37 M = 240.8 g/mol triethoxysilaneN,N,N′,N′-tetramethyl- 221.53 1.91 20.09 M = 116.21 g/molethylenediamine Completely ion-free water: 1st addition 200.27 18.16 2ndaddition 79.82 7.24 3rd addition 200.14 18.15 Σ inputs 1102.95 m(ethanol ex hydrolysis) = 229.4 g; final weight of product: 859.24 g,theory: 873.55 g; final weight of distillate: 1073.13 g

Procedure:

-   1. Reaction (duration about 9.7 h): Chloropropyltriethoxysilane is    initially charged and tetramethylethylenediamine is rapidly added    with stirring. This is followed by the 1st addition of water within    about 20 minutes (volume stream about 4.8 l/h) under vigorous    stirring. The pot contents are distinctly cloudy and then heated    under reflux (about 84-92° C.) for 6 h. The 2nd addition of water is    then made into the now clarified pot contents. After a further 1.5 h    of heating under reflux, the 3rd addition of water is made with    stirring during about 20 minutes, (volume stream about 4.8 l/h).-   2. Distillation: At a pot temperature of 48° C. to 53° C., then, the    hydrolysis ethanol and the excess TMEDA are distilled off under    reduced pressure (100-270 mbar). During the distillation, a total    859.02 g of water are returned. A clear low-viscosity liquid is    obtained.

Analyses:

Determination Result Theory Method Viscosity (20° C.) [mPa s] 43.8 DIN53015 Density (20° C.) [g/ml] 1.104 DIN 51757 Refractive index (20° C.)1.4184 DIN 51423 Color [mg Pt—Co/l] 70 ISO 6271 Solids [%] 48.3 DIN38409-1 pH 8.2 1:1 in water, DIN 38404-C5 SiO₂ [%] 11.6 11.4 see aboveEthanol after hydrolysis <0.1 see above [%] Total N [%] 4.6 6.1 seeabove Total chloride [%] 7.0 6.8 see above Hydrol. chloride [%] 7.0 6.8see above NMR: ¹H and ¹³C NMR spectra show the target product (thesilane is in a hydrolyzed and oligomerized state) as the main component(about 75% of the silane used): The formula hereinbelow is an idealizedempirical formula of the resulting solid on complete removal of thesolvent water and of the water formed by condensation.[(CH₃)₂N—CH₂—CH₂—N⁺(CH₃)₂CH₂—CH₂—CH₂—SiO_(1.5)]_(n)where n can formally be a number from 1 to ∞, preferably 4 to ∞.

In an aqueous solution, the polymeric product has silanol groups as wellas siloxane units.

In addition, small amounts of unconverted TMEDA and secondary signalsare observed. There are no pointers to CPTEO. Presumably, small amountsof TMEDA which is reacted 2 times are also present.

The ²⁹Si NMR spectrum shows: about 2 Si % of silanol(xOH), about 14 Si %of M-structures, about 51 Si % of D-structures, about 33 Si % ofT-structures.

Example 3

Waterborne VOC-free solution of a quaternary silane system prepared from3-chloropropyltriethoxysilane and tetramethylethylenediamine with excessof 3-chloropropyltriethoxysilane.

Apparatus: stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyltriethoxysilane 401.68 1.67 38.32 M = 240.8 g/ molN,N,N′,N′-tetramethyl- 164.53 1.42 15.70 M = 116.21 g/ ethylenediaminemol Completely ion-free water: 1st addition 201.45 19.22 2nd addition80.15 7.65 3rd addition 200.43 19.12 Σ inputs 1048.24 m (ethanol exhydrolysis) = 229.4 g; final weight of product after filtration: 771.70g, theory: 818.84 g; final weight of distillate: 377.65 g

Procedure:

-   1. Reaction (duration about 9.7 h): Chloropropyltriethoxysilane is    initially charged and tetramethylethylenediamine is rapidly added    with stirring. This is followed by the 1st addition of water within    about 18 minutes under vigorous stirring. The pot contents are    distinctly cloudy and then heated under reflux (about 82-84° C.) for    6 h. The 2nd addition of water is then made during 9 minutes into    the now clarified pot contents. After a further 1.6 h of heating    under reflux, the 3rd addition of water is made with stirring,    during about 13 minutes.-   2. Distillation: At a pot temperature of 52° C. to 60° C., then, the    hydrolysis ethanol is distilled off under reduced pressure (100-270    mbar). During the distillation, a total 859.02 g of water are    returned.-   3. Filtration: Thereafter, the slightly cloudy yellowish product is    filtered via pressure filter and Seitz K800. The resulting slightly    cloudy liquid is again filtered through a K700 filter. This gives a    clear slightly yellowish fluid.

Analyses:

Determination Result Theory Method Viscosity (20° C.) [mPa s] 88.2 DIN53015 Density (20° C.) [g/ml] 1.114 DIN 51757 Refractive index (20° C.)1.4239 DIN 51423 Color [mg Pt—Co/l] 65 ISO 6271 Solids [%] 51.4 DIN38409-1 pH 8.5 1:1 in water, DIN 38404-C5 SiO₂ [%] 12.5 12.2 see aboveEthanol after hydrolysis 0.2 see above [%] Total N [%] 4.6 4.8 see aboveTotal chloride [%] 7.6 7.3 see above Hydrol. chloride [%] 7.1 7.3 seeabove NMR: ¹H and ¹³C NMR spectra show the target product (the silane isin a hydrolyzed and oligomerized state) as the main component (about 65%of the silane used): The formula hereinbelow is an idealized empiricalformula of the resulting solid on complete removal of water (cf.corresponding remark in example 2).[(CH₃)₂N—CH₂—CH₂—N⁺(CH₃)₂CH₂—CH₂—CH₂—SiO_(1,5)]_(n)

In an aqueous solution, the polymeric product has silanol groups as wellas siloxane units.

In addition, unconverted TMEDA and secondary signals are observed. Thereare no pointers to CPTEO. Presumably, TMEDA which is reacted 2 times isalso present.

The ²⁹Si NMR spectrum shows: about 2 Si % of silanol(xOH), about 12 Si %of M-structures, about 46 Si % of D-structures, about 40 Si % ofT-structures.

Example 4

Waterborne VOC-free solution of a quaternary silane system prepared fromchloropropyltriethoxysilane and tetramethylethylenediamine. As aprocedural change, the total amount of water was added in one portion.

Apparatus: Stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyltriethoxysilane 399.8 1.66 45.77 M = 240.8 g/ molN,N,N′,N′-tetramethyl- 193.3 1.66 22.13 M = 116.21 g/ ethylenediaminemol Completely ion-free water 280.44 32.10 Σ inputs 873.54

Procedure: A 2 l four-neck flask stirred apparatus is initially chargedwith CPTEO and TMEDA under agitation. The completely ion-free water isadded dropwise at room temperature during 13 min. Severe cloudinessensues. At a pot temperature of 82-86° C., the contents are heated underreflux for 5.5 h to obtain a liquid containing a white precipitate(insoluble in ethanol or water).

Example 5

Waterborne solution of a quaternary silane system prepared from3-chloropropyltriethoxysilane and N,N-dimethylethylenediamine.

Apparatus:

Stirred reactor with reflux condenser, pot thermometer, top thermometerand metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyl- 107.79 0.448 34.1 M = 240.8 g/mol triethoxysilane N,N-39.44 0.447 12.5 M = 88.15 g/mol Dimethylethylenediamine Completelyion-free water 1st addition 41.4 13.1 2nd addition 40.0 12.7 3rdaddition 47.1 14.9 4th addition 40.0 12.7 Σ inputs 315.7

m(ethanol after hydrolysis)=61.8 g; final weight of product: 185.4 g,theory: 315.7 g

Procedure: A 0.5 l four-neck flask stirred apparatus is initiallycharged with CPTEO and dimethylethylenediamine under agitation. 41.4 gof completely ion-free water are added dropwise (1st addition) at roomtemperature within 5 min. Severe cloudiness ensues and the reaction isslightly exothermic. This is followed by refluxing at a pot temperatureof 83 to 85° C. for 4 h and the metered addition of the water duringthis period in a further three portions to obtain a slightly milkycloudy low-viscosity liquid.

Analyses:

Determination Result Method pH 9.2 DIN 38404-C5 SiO₂ [%] 6.6 see aboveTotal N [%] 3.1 see above Total chloride [%] 4.1 see above Hydrol.chloride [%] 3.6 see above

Example 6

Waterborne VOC-free solution of quaternary silane system prepared from3-chloropropyltrimethoxysilane (CPTMO) and tetramethylethylenediamine.

Apparatus: Stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] Comment Dynasylan ®CPTMO 330.5 1.67 35.84 M = 199.0 g/mol N,N,N′,N′-tetramethyl- 193.9 1.6721.03 M = 116.21 g/mol ethylenediamine Completely ion-free water 1staddition 199.8 21.67 2nd addition 79.95 8.67 3rd addition 100.1 10.864th addition 17.8 1.93 Σ inputs 922.05 m (ethanol ex hydrolysis) =160.52 g; final weight of product after filtration: 648.1 g, theory:761.63 g; final weight of distillate: 224.4 g

Procedure: A 1 l four-neck flask stirred apparatus is initially chargedwith CPTMO and TMEDA under agitation. Everything is stirred at 71 to 75°C. for 1.5 h. Thereafter, 199.8 g of completely ion-free water are addeddropwise at 71 to 87° C. during 2.4 h to form a slightly cloudyyellowish liquid. During the dropwise addition, the hydrolysis methanolwas distilled off under reduced pressure. Then, 79.95 g of completelyion-free water are added dropwise during about 16 min. The next day,100.1 g of completely ion-free water are added dropwise at a pottemperature of 35° C. to 39° C. during 3 minutes and residual quantitiesof hydrolysis methanol are then distilled off under reduced pressure. Atthe end, a further 17.8 g of completely ion-free water are stirred in.Then, the slightly cloudy yellowish product is filtered via pressurefilter and Seitz K900 to obtain a clear viscose yellowish liquid.

Analyses:

Determination Result Method Viscosity (20° C.) [mPa s] 450 DIN 53015Density (20° C.) [g/ml] 1.129 DIN 51757 Solids [%] 56.9 QM-AA AS-FA-SL7001 pH 8.6 1:1 in water, DIN 38404-C5 SiO₂ [%] 14.1 see above Methanolafter hydrolysis [%] 1.5 see above Free methanol [%] 1.5 see above Totalchloride [%] 8.4 see above Hydrol. chloride [%] 8.4 see above NMR:Oligomerization is more pronounced (compared with CPTEO-TMEDA reaction).The spectra show the target product (the silane is present in hydrolyzedand oligomerized state) as the main component (about 65% of the silaneused).

The formula hereinbelow gives an idealized empirical formula of theresulting solid on complete removal of water (cf. corresponding remarkin example 2).

[(CH₃)₂N—CH₂—CH₂—N⁺(CH₃)₂CH₂—CH₂—CH₂—SiO_(1.5)]_(n)

In aqueous solution, the polymeric product has silanol groups as well assiloxane units.

TMEDA monoadduct=83.6% TMEDA bisadduct=16.4%

The ²⁹Si NMR spectrum shows: about 0.7% of silanol(xOH), about 9.0 Si %of M-structures, about 49.6 Si % of D-structures, about 40.7 Si % ofT-structures

Example 7

Waterborne VOC-free solution of a quaternary silane system prepared from3-chloropropyltrimethoxysilane and tetramethylethylenediamine usingtetramethyl-ethylenediamine in excess.

Apparatus: stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] Comment Dynasylan ®CPTMO 298.3 1.50 28.37 M = 199.0 g/mol N,N,N′,N′-tetramethyl- 261.8 2.2524.93 M = 116.21 g/mol ethylenediamine Completely ion-free water 1staddition 49.81 4.74 2nd addition 99.91 9.51 3rd addition 101.08 9.62 4thaddition 144.8 13.79 HCl w = 37% 94.57 9.00 Σ inputs 1050.27 m (ethanolex hydrolysis) = 144.18 g; final weight of product after filtration:697.9 g final weight of distillate: 308.9 g

Procedure: A 1 l four-neck flask stirred apparatus is initially chargedwith CPTMO and TMEDA under agitation. Everything is stirred at 60 to 70°C. for 1.5 h. Thereafter, 50 g of completely ion-free water are addeddropwise at 80 to 90° C. during 30 min. Thereafter, the system isallowed to react for 30 min and at the same time the resulting methanolis distilled off at normal pressure. Then, 2 further 100 g lots of waterare added dropwise during 30 min before the system is allowed to reactfor a further 30 min to form a clear solution as soon as cloudinessoccurs interrupt the addition of water and allow the system to react.After about 145 g of methanol/water have distilled off, the distillationis discontinued. The CPTMO conversion is determined as differencebetween w (total chloride) and w (hydr. chloride) CPTMO. After thereaction is ended, the mixture is neutralized with 37% of hydrochloricacid asserting a pH of 7 (exothermic). Then, methanol-water is distilledoff at 300 to 100 mbar and a pot temperature of up to about 55° C. Whenthe batch turns viscose, about 100 g of water are added (theoreticalamount of hydrolysis methanol for 1.5-molar batch: 144.2 g). About 290 gof methanol-water mixture should be distilled off. At the end, thedistillatively removed amount of water is added back. The product isfiltered through a SEITZ K900 pressure filter to obtain a clearyellowish slightly viscose liquid.

Analyses:

Determination Result Method Viscosity (20° C.) [mPa s] 286 DIN 53015Solids [%] 68.3 DIN 38409-1 pH 7.1 1:1 in water, DIN 38404-C5 SiO₂ [%]12.3 see above Methanol after hydrolysis [%] 0.1 see above Free methanol[%] 0.1 see above NMR: The spectra show the target product (the silaneis in a hydrolyzed and oligomerized state) as the main component (about85% of the silane used)

The formula hereinbelow gives an idealized empirical formula of theresulting solid on complete removal of water (cf. corresponding remarkin example 2).

[(CH₃)₂N—CH₂—CH₂—N⁺(CH₃)₂CH₂—CH₂—CH₂—SiO_(1.5)]_(n)

In aqueous solution, the polymeric product has silanol groups as well assiloxane units.

The ²⁹Si NMR spectrum shows: about 1.5% of silanol(xOH), about 8.4 Si %of M-structures, about 46.7 Si % of D-structures, about 43.4 Si % ofT-structures

Example 8

Waterborne VOC-free solution of a quaternary silane co-condensateprepared from 3-chloropropyltriethoxysilane,3-aminopropyltriethoxysilane (AMEO) and tetramethylethylenediamine

Apparatus: Stirred reactor with distilling device, pot thermometer, topthermometer, vacuum pump, manometer and metering device.

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] Commentchloropropyl- 200.1 0.83 35.61 M = 240.8 g/mol triethoxysilaneN,N,N′,N′-tetramethyl- 96.7 0.83 17.21 M = 116.21 g/mol ethylenediamineCompletely ion-free water 1st addition 100.0 17.80 2nd addition 40.17.14 3rd addition 100.1 17.81 Dynasylan ® AMEO 24.9 0.113 4.43 M = 221.0g/mol Σ inputs 561.9 m (ethanol ex hydrolysis) = 130.20 g, final weightof product: 413.3 g, theory: 431.7 g; final weight of distillate: 219.5g

Procedure: A 1 l four-neck flask stirred apparatus is initially chargedwith CPTEO and TMEDA under agitation. 100.0 g of completely ion-freewater are added dropwise (1st addition) at room temperature during 15min. Severe cloudiness ensues and the reaction is slightly exothermic.This is followed by refluxing at about 90° C. pot temperature for 3 h.Thereafter, Dynasylan® AMEO are added dropwise within about 15 minfollowed by a further 3 h of heating at about 90° C. pot temperature.Subsequently, 40.0 g of completely ion-free water are added (2ndaddition) during 5 min followed by a further 1.5 h of heating at 90° C.Finally, a further 100.0 g of completely ion-free water are added (3rdaddition) during 20 min under agitation.

Thereafter, ethanol/water is distilled off (twice the amount of ethanoltheoretically formed) at 300-100 mbar and a pot temperature up to about55° C. When the batch turns viscose, water is quickly added. Oncompletion of the distillation the distillatively removed amount ofwater is replaced with completely ion-free water and the mixture iscooled down to RT with stirring. The product is filtered through a SEITZK700 pressure filter to obtain a clear slightly yellow low-viscosityliquid.

Analyses:

Determination Result Method Viscosity (20° C.) [mPa s] 180 DIN 53015Density (20° C.) [g/ml] 1.117 DIN 51757 Color [mg Pt—Co/l] 160 ISO 6271Solids [%] 50.1 DIN 38409-1 pH 8.5 1:1 in water, DIN 38404-C5 SiO₂ [%]13.5 see above Ethanol after hydrolysis [%] 0.1 see above Total N [%]5.0 see above Total chloride [%] 7.0 see above Hydrol. chloride [%] 7.0see above

Example 9

Preparation of silanized silica dispersions and production ofpapercoating slips therefrom: substances: polyvinyl alcohol: partiallyhydrolyzed polyvinyl alcohol (from Poval® PVA 235); boric acid solution:7% by weight aqueous boric acid solution.

A general example of preparation: the silica used is a commerciallyavailable pyrogenous silica having a surface area of 200 m²/g, a primaryparticle size of about 12 nm and an SiO₂ content of >99.8% by weight.The pyrogenous silica is incorporated in the aqueous solution by meansof a Dispermat dissolver with heavy duty d=60 mm dissolver disk.Postdispersion is effected using an Ultra Turrax T25 rotor-statordisperser. The coating slip is produced in a glass beaker equipped witha stirring element (magnetic stirrer) from the aqueous silica dispersionby adding a 9.04% by weight aqueous solution of a partially hydrolyzedpolyvinyl alcohol from Kuraray, Poval® PVA 235, degree of hydrolysis87-89%, viscosity 80-110 mPa s, and a 7% by weight aqueous solution ofboric acid.

Example 9a

Coating slip using butylaminopropyltrimethoxysilane:

-   1. Preparation of silanized silica dispersion: 600.13 g of    completely ion-free water and 10.0 g of an aqueous 18% by weight HCl    solution are initially charged. A dissolver is used to disperse    248.41 g of pyrogenous silica. This is followed by 10 min    postdispersal at 8000-10 000 rpm. This is followed by a further    homogenization for 10 min using Ultra Turrax at 20 500 rpm. Then,    17.14 g of a 20% by weight solution of    butylaminopropyltrimethoxysilane in methanol are gradually added    together with a further 4.03 g of the 18% by weight hydrochloric    acid. In the process, the pH must not exceed a value of about 4,    since the dispersion turns very viscose above that value. On    completion of the silane addition the mixture is further dispersed    for about 60 min using Ultra Turrax at 20 500 rpm.-   2. Production of a coating slip from 1: 65.15 g of completely    ion-free water are initially charged. 74.86 g of the polyvinyl    alcohol solution are added with stirring. Then, 124.97 g of the    silica dispersion from 1 are stirred in. Thereafter, 12.03 g of the    boric acid solution are metered in during 10 min. This is followed    by 15 min of stirring. The coating slip has properties reported in    the table “Properties of coating slip”.

Example 9b

Coating slip using an aqueous alcohol-free hydrolyzate ofbutylaminopropyl-trimethoxysilane.

The hydrolyzate is prepared as follows:

Apparatus: 1 l four-neck flask, stirring mechanism equipped with bladestirrer, dropping funnel, thermometer, distillation bridge with vacuumconnection, receiver, vacuum pump stand, oil bath with regulator

Materials Used:

Amount of m (actual) substance W/W Inputs [g] [mol] [%]Butylaminopropyltrimethoxysilane 249.53 g 1.06 mol   50% Formic acid 85% 68.10 g 1.48 mol + 13.7% 40.6% excess Completely ion-free water 181.15g 10.6 mol 36.3% Total Σ  498.8 g

Procedure: completely ion-free water and formic acid are initiallycharged with stirring and butylaminopropyltrimethoxysilane is addeddropwise such that the pot temperature does not exceed 60° C. Oncompletion of the dropwise addition the pH is measured. It should bebetween pH 4.0-5.0. Add formic acid or butylaminopropyltrimethoxysilaneif necessary. This is followed by stirring with the oil bath at a pottemperature of 60° C. for 3 h. Before the methanol is distilled off,101.9 g of water are added in order that the distillatively removedmethanol may be replaced in terms of volume. At a pressure of 130 mbarand a pot temperature of 40-60° C., 203.8 g of methanol/water aredistilled off. Then, the final weight of the pot contents are determinedand completely ion-free water is added to restore the original mass of499.0 g.

Analyses (Product):

Determination Result Method Total N: 2.8% (mass) see above Si content:5.9% (mass) 1H NMR: per n-butylaminosilyl radical: 1.2 mol of formate,0.05 mol of methanol 29Si NMR: 1% of monomers 5% of Si-M- 37% of Si-D-57% of Si-T-structures pH: 4.6 DIN 38404 Solids content: 44.0% (mass)Cf. QM-AA Viscosity (20° C.) 27.9 mPa s DIN 53015 Methanol afterhydrolysis 0.6% (mass) see above Free methanol 0.6% (mass) SiO₂ content12.7% (mass) see above Density (20° C.) 1.012 g/cm3 DIN 51757

-   1. Preparation of silanized silica dispersion: 600.02 g of    completely ion-free water and 5.95 g of an aqueous 18% by weight HCl    solution are initially charged. A dissolver is used to disperse    260.84 g of pyrogenous silica. This is followed by 15 min    postdispersal at 5000-7000 rpm. This is followed by a further    homogenization for 10 min using Ultra Turrax at 20 500 rpm. Then,    34.16 g of the silane hydrolyzate are gradually added with a further    1.37 g of the 18% by weight hydrochloric acid. In the process, the    pH must not exceed a value of about 3, since the dispersion turns    very viscose above that value. On completion of the silane addition    the mixture is further dispersed for about 60 min using Ultra Turrax    at 20 500 rpm.-   2. Production of a coating slip from 1: 65.52 g of completely    ion-free water are initially charged. 75.30 g of the polyvinyl    alcohol solution are added with stirring. Then, 125.42 g of the    silica dispersion from 1 are stirred in. Thereafter, 12.00 g of the    boric acid solution are metered in during 10 min. This is followed    by 15 min of stirring. The coating slip has properties reported in    the table “Properties of coating slip”.

Example 9c

Coating slip using an aqueous alcohol-free hydrolyzate ofbutylaminopropyl-trimethoxysilane.

The hydrolyzate is prepared as described under example 9b.

-   1. Preparation of silanized silica dispersion: 600.62 g of    completely ion-free water are initially charged. A dissolver is used    to disperse 259.45 g of pyrogenous silica. This is followed by 15    min postdispersal at 5000-7000 rpm. This is followed by a further    homogenization for 10 min using Ultra Turrax at 20 500 rpm.    Thereafter, 4.82 g of an 85% by weight formic acid solution in water    are added. Then, 68.59 g of the silane hydrolyzate are gradually    added. In the process, the pH must not exceed a value of about 4,    since the dispersion turns very viscose above that value. On    completion of the silane addition the mixture is further dispersed    for about 60 min using Ultra Turrax at 20 500 rpm.-   2. Production of a coating slip from 1: 65.11 g of completely    ion-free water are initially charged. 75.35 g of the polyvinyl    alcohol solution are added with stirring. Then, 125.34 g of the    silica dispersion from 1 are stirred in. Thereafter, 12.08 g of the    boric acid solution are metered in during 10 min. This is followed    by 15 min of stirring. The coating slip has properties reported in    the table “Properties of coating slip”.

Example 9d

Coating slip using the aqueous alcohol-free quaternary aminosilanesystem from example 1:

-   1. Preparation of silanized silica dispersion: 300.04 g of    completely ion-free water and 7.07 g of an aqueous 18% by weight HCl    solution are initially charged. A dissolver is used to disperse    129.34 g of pyrogenous silica. This is followed by 15 min    postdispersal at 4000 rpm. This is followed by a further    homogenization for 10 min using Ultra Turrax at 20 500 rpm. Then,    31.20 g of the silane hydrolyzate are gradually added with a further    1.65 g of the 18% by weight hydrochloric acid. In the process, the    pH must not exceed a value of about 3, since the dispersion turns    very viscose above that value. On completion of the silane addition    the mixture is further dispersed for about 60 min using Ultra Turrax    at 20 500 rpm.-   2. Production of a coating slip from 1: 65.00 g of completely    ion-free water are initially charged. 76.08 g of the polyvinyl    alcohol solution are added with stirring. Then, 127.25 g of the    silica dispersion from 1 are stirred in. Thereafter, 12.05 g of the    boric acid solution are metered in during 10 min. This is followed    by 15 min of stirring. The coating slip has properties reported in    the table “Properties of coating slip”.

Example 9e

Coating slip using an alcohol-containing quaternary aminosilane.

The quaternary aminosilane is prepared as follows:

Water-free ethanolic quaternary silane system prepared fromchloropropyltriethoxysilane and tetramethylethylenediamine.

Apparatus: Büchi autoclave with pot thermometer, manometer and N2blanket

Materials Used:

m n w (input) (inputs) (inputs) Inputs [g] [mol] [%] CommentChloropropyl- 216.7 0.9 25.7 M = 240.8 g/mol triethoxysilane N,N,N′,N′-104.6 0.9 12.4 M = 116.21 g/mol tetramethyl- ethylenediamine Ethanol520.7 61.8

Final weight of product: 718.0 g, theory: 751.3 g; total amount ofsamples: 90.7 g

Procedure:

Chloropropyltriethoxysilane is initially charged, andtetramethylethylenediamine and ethanol are rapidly added with stirring.The reaction is then carried out in the autoclave at a pot temperatureof 140° C. The overpressure rises to about 4.3 bar in the process. Thereaction is policed time-dependently using GC. Extending the reactiontime from 5 h to 10 h leads to a distinct reduction inchloropropyltriethoxysilane at almost constant TMEDA content: reactionas far as the bisadduct. A conversion of >90% was reached after areaction time of 10 h. White precipitations formed to a minimal extentin the pot. They were filtered off, washed with n-heptane and dried in arotary evaporator: m=5.0 g.

Analyses (product):

Determination Result Method Density (20° C.) [g/ml] 0.856 DIN 51757 SiO₂[%] 6.6 see above Total N [%] 2.8 see above Total chloride [%] 3.5 seeabove Hydrol. chloride [%] 3.5 see above

-   1. Preparation of silanized silica dispersion: 600.33 g of    completely ion-free water and 9.65 g of an aqueous 18% by weight HCl    solution are initially charged. A dissolver is used to disperse    248.79 g of pyrogenous silica. This is followed by 15 min    postdispersal at 6000 rpm. This is followed by a further    homogenization for 10 min using Ultra Turrax at 20 500 rpm. Then,    66.81 g of the ethanolic silane solution are gradually added    together with a further 4.57 g of 18% by weight hydrochloric acid.    In the process, the pH must not exceed a value of about 3.5, since    the dispersion turns very viscose above that value. On completion of    the silane addition the mixture is further dispersed for about 60    min using Ultra Turrax at 20 500 rpm.-   2. Production of a coating slip from 1: 64.94 g of completely    ion-free water are initially charged. 75.81 g of the polyvinyl    alcohol solution are added with stirring. Then, 126.95 g of the    silica dispersion from 1 are stirred in. Thereafter, 12.04 g of the    boric acid solution are metered in during 10 min. This is followed    by 15 min of stirring. The coating slip has properties reported in    the table which follows.

Table of “Properties of coating slips”: Example 9a 9b 9c 9d 9e Silanecontent of silica dispersion/ 1.8 1.9 3.7 3.7 1.9 wt % Alcohol contentof silica dispersion/ 7.9 0.0 0.0 0.0 6.4 wt % Viscosity of coatingslip/mPa s 129 589 174 83 423

It is evident from the table that alcoholic aminosilane solutions(example 9a) can be used to obtain low-viscosity coating slips having aviscosity <150 mPa s. Using the same silane in the form of thewaterborne alcohol-free hydrolyzate provides acceptable viscositiesbelow 300 mPa s only at nearly double the dose (example 9c). Whenwaterborne quaternary aminosilane solutions are used (example 9d), thesame dose (comparison with waterborne aminosilane) provides excellentviscosities below 100 mPa s. The same active silane substance, bycontrast, when used as nonhydrolyzed alcoholic solution, provides anonacceptable viscosity to the coating slip and also a high, problematicalcohol content.

1. A process for preparing a composition containing quaternaryamino-functional organosilicon compounds, characterized in that itcomprises reacting as component A (i) at least one haloalkyl-functionalalkoxysilane of the general formula I(R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂Hal]_(1+y)  (I), where the R¹ groupsare the same or different and R¹ represents a hydrogen, a linear,branched, or cyclic alkyl group having 1 to 8 carbon atoms, an aryl,arylalkyl or acyl group, the R² groups are the same or different and R²represents a linear, branched or cyclic alkyl group having 1 to 8 carbonatoms, or an aryl, arylalkyl or acyl group, the R³ groups are the sameor different and R² signifies a linear, branched or cyclic alkylenegroup having 1 to 18 carbon atoms, n is equal to 0 or 1 and Halrepresents chlorine or bromine, and x is equal to 0, 1 or 2, y is equalto 0, 1 or 2 and (x+y) is equal to 0, 1 or 2, or (ii) a hydrolysis orcondensation product of at least one alkoxysilane of the aforementionedgeneral formula I or (iii) a mixture of at least one alkoxysilane of theaforementioned general formula I and a hydrolysis and/or condensationproduct of at least one alkoxysilane of the aforementioned generalformula I with a tertiary amine of the general formula II as componentB,N(R⁴)₃  (II), where the R⁴ groups are the same or different and R⁴represents a group (R¹0)_(3-x-y)(R²)_(x)Si[(R³)_(n)CH₂—]_(1+y), whereR¹, R², R³, n, x, y and (x+y) likewise have the aforementioned meaning,or represents a linear, branched or cyclic alkyl group having 1 to 30carbon atoms which may additionally be substituted, where optionally twoR⁴ groups are in turn linked together and combine with the nitrogen ofthe tertiary amine to form a cycle, in the presence of a defined amountof water, and removing the resulting hydrolysis alcohol at leastpartially from the system.
 2. The process according to claim 1,characterized in that the reaction is carried out in the presence of acatalyst and/or under addition of a separate catalyst.
 3. The processaccording to claim 1, characterized in that there is used as a furtherinput component C at least one further hydrolyzable/condensable siliconcompound, its hydrolysis, homo-, co-, block co-condensate or mixturesthereof.
 4. The process according to claim 1, characterized in thatwater is used in an amount of 0.5 to 500 mol of water per mole ofsilicon atoms present in the reaction mixture, concerning the usedcomponents A and also optionally B and/or C.
 5. The process according toclaim 1 any one of claims 1 to 4, characterized in that the water ismetered continuously or discontinuously into the reaction mixture of theinput components A, B and optionally C.
 6. The process according toclaim 1, characterized in that the reaction is carried out at a pressurein the range from 1 mbar to 1.1 bar.
 7. The process according to claim1, characterized in that volatile solvent/diluent medium and any groupshydrolyzable to volatile solvent, more particularly hydrolysis alcohol,are removed down to a level in the overall composition of below 12% byweight to 0% by weight, wherein the removing of volatile solvent/diluentmedium can be effected during the reaction and/or thereafter bydistillation.
 8. The process according to claim 1, characterized in thatcomponent A comprises at least one silicon compound from the series3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,3-chloropropyl-methyldimethoxysilane,3-chloropropylmethyldiethoxysilane, 3-chloropropyl-dimethylethoxysilaneor 3-chloropropyldimethylmethoxysilane or a hydrolysis or condensationproduct of the aforementioned alkoxysilanes.
 9. The process according toclaim 1, characterized in that component B comprises at least onetertiary amine selected from the series of compounds of formulae IIaand/or IIb,(R¹⁴)₂N[CH₂CH₂N(R¹⁴)]_(h)CH₂CH₂N(R¹⁴)₂  (IIa), where R¹⁴ in eachoccurrence independently represents a branched, unbranched or cyclicalkyl, aryl or alkylaryl group having 1 to 20 carbon atoms and h isequal to 0, 1, 2, 3, 4, 5, 6 or 7,[(CH₃)—(CH₂)_(w)]_(p*)N(R¹⁴)_(3-p*)  (IIb), where w is equal to 2 to 20,more particularly where w is equal to 7 to 17, and R¹⁴ in eachoccurrence independently represents a branched, unbranched or cyclicalkyl, aryl or alkylaryl group having 1 to 20 carbon atoms and p* isequal to 1 or
 2. 10. The process according to claim 1, characterized inthat component B comprises at least one tertiary amine selected from theseries tetramethylethylenediamine, pentamethyldiethylenetriamine,hexadecyldimethylamine, octadecyldimethylamine, tetradecyldimethylamine,dodecyldimethylamine, decyldimethylamine, octyldimethylamine,tetraethylethylenediamine, pentaethyldiethylenetriamine,hexadecyldiethylamine, octadecyldiethylamine, tetradecyldiethylamine,dodecyldiethylamine, decyldiethylamine, octyldiethylamine,isohexadecyldimethylamine, isooctadecyldimethylamine,isotetradecyldimethylamine, isododecyldimethylamine,isodecyldimethylamine, isooctyldimethylamine,isotetraethylethylenediamine, isopentaethyldiethylenetriamine,isohexadecyldiethylamine, isooctadecyldiethylamine,isotetradecyldiethylamine, isododecyldiethylamine, isodecyldiethylamine,isooctyldiethylamine, tris(trimethoxysilylpropyl)amine,tris(triethoxysilylpropyl)amine, tris(trimethoxysilylmethyl)amine,tris(triethoxysilylmethyl)amine.
 11. The process according to claim 1,characterized in that components A and B are used in a ratio, whereinthe molar ratio of the silicon compound within the meaning of formulaIto the tertiary amine compound within the meaning of formula II is inthe range from 2:1 to 1:m, wherein m is the number of tertiary aminegroups of formula II and m is an integer between 1 to
 100. 12. Theprocess according to claim 1, characterized in that components A and Care used in a molar ratio of 1:<4.
 13. The process according to claim 1,characterized in that component C comprises at least one furtherorganofunctionalized silicon compound of formula III, its hydrolysisproducts, condensation products, co- or block condensation products ormixtures thereof,(R⁷0)_(3-a-b)(R⁸)_(a)Si(B)_(1+b)  (III) where R⁷ in each occurrenceindependently represents a hydrogen, a linear, branched or cyclic alkylgroup having 1 to 8 carbon atoms, an aryl, arylalkyl or acyl group, R⁸in each occurrence independently signifies a linear, branched or cyclicalkyl group having 1 to 24 carbon atoms, an aryl or arylalkyl group, theB groups are the same or different and B represents an organofunctionalgroup, a is equal to 0, 1 or 2, b is equal to 0, 1 or 2 and (a+b) isequal to 0, 1 or 2, wherein the compound of the general formula III isselected from compounds with B being equal to —[(R¹⁰)_(n)R⁹], where R¹⁰represents a linear, branched or cyclic alkylene group having 1 to 18carbon atoms or an alkenylene group having 1 to 18 carbon atoms, n isequal to 0 or 1 and R⁹ in each occurrence independently signifies asubstituted or unsubstituted linear, branched or cyclic alkyl grouphaving 1 to 30 carbon atoms which may optionally include one or more—N(R^(3*))₂, —OR^(3*) and/or —SR^(3*) groups, with R^(3*) in eachoccurrence independently representing a hydrogen or with R^(3*) equal R⁹and also R⁹ together with a heteroatom N, S or O being a cycle orheteroaromatic having 1 to 7 carbon atoms, B being equal to(R^(5*)0)_(3-x*)(R^(6*))_(x*)Si[(R^(2*))CH₂—], where R^(5*) in eachoccurrence independently represents a hydrogen, a linear, branched orcyclic alkyl group having 1 to 8 carbon atoms or represents an aryl,arylalkyl or acyl group, R^(6*) in each occurrence independentlysignifies a linear, branched or cyclic alkyl group having 1 to 24 carbonatoms or an aryl, arylalkyl or acyl group, R^(2*) is a linear, branchedor cyclic alkylene group having 1 to 18 carbon atoms or an alkenylenegroup having 1 to 18 carbon atoms, with n* being equal to 0, 1 or 2 andalso —CH₂CH(CH₃)—, and x* is equal to 0, 1 or 2, B is a primary,secondary or tertiary amino-functional radical of the general formulaeIIIa or IIIb,R¹¹_(h*)NH_((2-h*))[(CH₂)_(h)(NH)]_(j)[(CH₂)_(l)(NH)]_(c)—(CH₂)_(k)—  (IIIa)where 0≦h≦6; h*=0, 1 or 2, j=0, 1 or 2; 0≦l≦6; c=0, 1 or 2; 0≦k≦6 andR¹¹ corresponds to a benzyl, aryl, vinyl, formyl radical or a linear,branched or cyclic alkyl radical having 1 to 8 carbon atoms and informula Mb[NH₂(CH₂)_(d)]₂N(CH₂)_(p)—  (IIIb) 0≦d≦6 and 0≦p≦6, B is equal to—(CH₂)_(i*)—[NH(CH₂)_(f*)]_(g*)NH[(CH₂)_(f*)NH]_(g*)—(CH₂)_(i*)—SiR²*_(a*)(OR^(1**))_(b*)(IIIc),where i*, f* or g* in formula IIIc are each independently identical ordifferent, with i*=0 to 8, f*=1, 2 or 3, g*=0, 1 or 2 and R^(1**)corresponding to a linear, cyclic or branched alkyl radical having 1 to4 carbon atoms, where i* is more particularly one of the numbers 1, 2, 3or 4, with a*, b*=0, 1, 2 or 3 and (a*+b*) equal 3 and R^(2*) is analkyl radical having 1 to 24 carbon atoms, B is a radicalR¹²—Y_(q)—(CH₂)_(s)—, where R¹² corresponds to a mono-, oligo- orperfluorinated alkyl radical having 1 to 20 carbon atoms or to a mono-,oligo- or perfluorinated aryl radical, where Y further corresponds to a—CH₂—, —O—, -aryl or —S— radical and q is =0 or 1 and s is =0 or 2, moreparticularly B corresponds to a perfluorinated alkyl radical having 1 to20 carbon atoms, B is a vinyl, allyl, isopropenyl radical, mercaptoalkylradical, sulfanealkyl radical, ureidoalkyl radical, acryloyloxyalkylradical, methacryloyloxyalkyl radical, more particularlymethacryloyloxypropyl, or a linear, branched or cyclic alkoxy radicalhaving 1 to 24 carbon atoms, B is a hydroxyalkyl, epoxy and/or etherradical, more particularly a 3-glycidyloxyalkyl, 3-glycidyloxypropyl,dihydroxyalkyl, epoxyalkyl, epoxycycloalkyl, polyalkylglycolalkylradical or a polyalkylglycol-3-propyl radical, or at least partialhydrolysis and condensation products of one or at least two compounds offormula III.
 14. The process according to claim 1, characterized in thatcomponent C comprises at least one silicon compound from the seriessilicon tetrachloride, tetramethoxysilane, tetraethoxysilane,tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-butyltrimethoxysilane,i-butyltrimethoxysilane, n-butyltriethoxysilane, i-butyltriethoxysilane,n-octyltrimethoxysilane i-octyltrimethoxysilane, n-octyltriethoxysilane,i-octyltriethoxysilane, hexadecyltrimethoxysilane,hexadecyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(2-methoxyethoxy)silane, phenyltrimethoxysilane,phenyltriethoxysilane,tridecafluoro-1,1,2,2-tetrahydro-octyltrimethoxysilane,tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,1-mercaptomethyltrimethoxysilane, 1-mercaptomethyltriethoxysilane,3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane,3-methacryloxyisobutyltrimethoxysilane,3-methacryloxyisobutyltriethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane,3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-aminopropyl-methyldimethoxysilane,3-aminopropylmethyldiethoxysilane, 1-aminomethyl-trimethoxysilane,1-aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane,2-aminoethyltriethoxysilane, 3-aminoisobutyltrimethoxysilane,3-aminoisobutyltriethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane,N-n-butyl-3-aminopropylmethyldiethoxysilane,N-n-butyl-3-aminopropyltrimethoxysilane,N-n-butyl-3-aminopropylmethyldimethoxysilane,N-n-butyl-1-aminomethyltriethoxysilane,N-n-butyl-1-aminomethylmethyldimethoxysilane,N-n-butyl-1-aminomethyltrimethoxysilane,N-n-butyl-1-aminomethylmethyltriethoxysilane,benzyl-3-aminopropyltrimethoxysilane,benzyl-3-aminopropyltriethoxysilane,benzyl-2-aminoethyl-3-aminopropyltrimethoxysilane,benzyl-2-aminoethyl-3-aminopropyltriethoxysilane,N-formyl-3-aminopropyltriethoxysilane,N-formyl-3-aminopropyltrimethoxysilane,N-formyl-1-aminomethylmethyldimethoxysilane,N-formyl-1-aminomethylmethyldiethoxysilane,diaminoethylene-3-propyltrimethoxysilane,diaminoethylene-3-propyltriethoxysilane,triaminodiethylene-3-propyltrimethoxysilane,triaminodiethylene-3-propyltriethoxysilane,(2-aminoethylamino)ethyltrimethoxysilane,(2-aminoethylamino)ethyltriethoxysilane,(1-aminoethylamino)methyltrimethoxysilane,(1-aminoethylamino)methyltriethoxysilane,tris(trimethoxysilylpropyl)amine, tris(triethoxysilylpropyl)amine,tris(trimethoxysilylmethyl)amine, tris(triethoxysilylmethyl)amine,bis(trimethoxysilylpropyl)amine, bis(triethoxysilylpropyl)amine,bis(diethoxymethylsilylpropyl)amine,bis(dimethoxymethylsilylpropyl)amine, bis(triethoxysilylmethyl)amine,bis(trimethoxysilylmethyl)amine, bis(diethoxymethylsilylmethyl)amine,bis(dimethoxymethylsilylmethyl)amine,(H₃CO)₃Si(CH₂)₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃,(H₃CO)₃Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃,(H₃CO)₂(CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₂(CH₃), (H₃CO)₃(CH₃)Si(CH₂)₃NH(CH₂)₂NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₂ (CH₃), or a mixture of atleast two of the aforementioned compounds or a hydrolysis/condensationproduct of one of the aforementioned compounds or a hydrolysis,condensation, co-, block or block co-condensation product of at leasttwo of the aforementioned compounds.
 15. The process according to claim1, characterized in that the components A and B and optionally C aremixed, wherein the mixture may optionally have added to it asolvent/diluent medium, water is continuously or discontinuously meteredinto the mixture in an amount of 0.5 to 500 mol of water per mole ofsilicon atoms present, and optionally a catalyst is added to thereaction mixture, the reaction mixture present is set to a temperaturebetween 20 and 150° C. at ambient pressure or reduced pressure, and theresultant hydrolysis alcohol is at least partially removed from thereaction mixture as is any solvent/diluent medium used, and thecomposition thus obtained is optionally diluted with water, andthereafter optionally admixed or contacted with at least one furthercomponent from the series of pigments, fillers, binders, crosslinkers,optical brighteners, thickeners, rheological auxiliaries, coatingauxiliaries or some other auxiliary.
 16. A composition containingquaternary aminoalkyl-functional organosilicon compounds and water,obtainable by a process according to claim
 1. 17. The compositionaccording to claim 16, characterized by a level of active ingredient inthe composition ranging from 0.1% to 99.9% by weight, wherein all theconstituents in the composition sum to 100% by weight.
 18. Thecomposition according to claim 16, characterized by a level of waterranging from 0.0999% to 99.9% by weight and a level of volatilesolvent/hydrolysis alcohol in the overall composition of below 12% byweight to 0% by weight, wherein all the constituents in the compositionsum to 100% by weight.
 19. The composition according to claim 16,characterized in that the composition contains at least one further ofthe following components from the series pigments, fillers, binders,crosslinkers, optical brighteners, coating auxiliaries or otherauxiliaries.
 20. The composition according to claim 16, characterized inthat the composition has a viscosity of <1500 mPa s.
 21. The use of acomposition according to claim 16 for modification, treatment and/orproduction of formulations, substrates, articles, organic or inorganicmaterials, composite materials, papercoating slips, inkjet applications,papercoating materials, paper, textiles, fillers, biocidally,fungicidally and/or virucidally acting formulations, biocidally,fungicidally and/or virucidally acting coatings, for finishing of fibermaterials, yarns and/or textiles, for textile impregnation, forantistatisization of surfaces, more particularly sheetlike, fibrous,woven, granular and/or pulverulent materials.